A printable polymer sheet and its application

Abstract

The present invention relates to a printable polymer sheet and its application, wherein the raw material is mainly polyethylene with a gram weight of 46 to 76 g / m 2 ; The surface strength of the positive printing is greater than 3.4m / s; the surface strength of the reverse printing is greater than 2.8m / s; the smoothness is 25 to 50 seconds; the burst resistance index is 6 to 12kPa·m 2 / g. The present application utilizes the addition of inorganic substances to improve the printability of the sheet, and utilizes the high toughness of PBT itself to improve the technical problem of poor printability caused by insufficient toughness of polyethylene sheets; the polymer sheet prepared by flash evaporation has excellent waterproof and breathable properties, isolating chemical liquids, dry and wet particles, and its physical properties are not affected by immersion in water. Therefore, it can be used as various high-grade papers such as book paper, map paper, and coin paper, such as for making field maps, military charts, outdoor posters, flags, etc. It is not afraid of wind and rain, and is an ideal material for use in harsh environments.

Description

[Technical field]

[0001] The invention relates to the technical field of flash spinning, in particular to a printable polymer sheet and its application. [Background technology]

[0002] Flash spinning of ultrafine fibers is to dissolve the fiber-forming polymer under high temperature and high pressure conditions to prepare a homogeneous spinning solution of a certain concentration, and then put the prepared homogeneous spinning solution into a low-pressure chamber under the action of high pressure. Due to the slight decrease in pressure, incomplete phase separation occurs, and then the spinning solution quickly passes through the spinneret hole, and expands rapidly at the spinneret hole. The solvent undergoes a phase change to become steam and rapidly separates from the polymer, and forms a supersonic steam flow. The polymer is thus broken and stretched at high speed by the supersonic steam flow. In this process, the solvent needs to absorb a large amount of heat, so that the polymer quickly crystallizes and cools into highly oriented ultrafine fiber filaments. Then, the impact force of the high-speed solvent airflow is used to send the ultrafine fiber filaments to a rotating dispersion disk. Due to the blocking effect of the rotating dispersion disk, the ultrafine fiber filaments change direction and move toward the conveyor belt below. Finally, an electrostatic field is applied to the ultrafine fiber filaments through the corona discharge method, so that the ultrafine fiber filaments are charged with the same electrostatic charge, which repel each other and disperse during the stretching process. The mesh ultrafine fiber filaments after fiber opening are stacked and laid through a swing device to meet the product design requirements. The obtained fiber web is bonded and reinforced in different ways to obtain flash-steamed sheets of different styles. At present, there is a technical problem that flash-steamed sheets have high strength but are difficult to print. This application improves the printing problem of flash-steamed sheets through raw materials and processes. Regarding patents for flash-steamed sheets, most of the applicants are DuPont; some patents are listed below to analyze the characteristics of DuPont patents, that is, defining products by physical parameters.

[0003] Chinese patent publication number CN112423978A relates to a conformable polyethylene fabric and articles made therefrom, wherein the sheet has a width of at least 10 mm and a plurality of punctures, wherein each puncture is separated from every other puncture by a distance of at least 1 mm, and wherein the fabric has an average sound velocity exceeding 2500 m / s.

[0004] Chinese patent publication number CN109070534B relates to a composite ballistic-resistant laminate comprising a plurality of cross-ply sheets, each cross-ply sheet further comprising (i) first and second fibrous or non-fibrous ultra-high molecular weight polyethylene layers and (ii) first and second thermoplastic adhesive layers, each adhesive layer having a basis weight of no more than 5 gsm, wherein the thermoplastic adhesive has a zero shear rate viscosity of at least 1500 Pa-s as measured by ASTM D4440, and wherein (a) the polyethylene layers and thermoplastic adhesive layers alternate within the sheet, (b) greater than 50% of the polyethylene layers are arranged such that the orientation of the first polyethylene layer is offset relative to the orientation of the second polyethylene layer, and (c) the plurality of cross-ply sheets form a stack that, when subjected to compaction at a pressure of 255 bar and a temperature of 132° C., does not suffer a pressure loss of greater than 8 bar within the first two minutes of compaction under the test method.

[0005] Chinese patent publication number CN106574401B relates to flash-spun plexifilamentary strands and sheets, including flash-spun plexifilamentary fiber strands, which contain fibers having a total crystallinity index of less than or equal to 55%, and the flash-spun plexifilamentary fiber strands have a BET surface area of ​​less than or equal to 12 m2 / g and an extrusion value of greater than or equal to 0.9 mm / g, wherein the fiber strands mainly contain fibers formed from homopolymers of ethylene; wherein the fiber strands mainly contain the fibers, which are formed from high-density polyethylene and have a surface area as determined by X-ray. The sheet is produced by a flash spinning process using a spinning agent medium comprising a mixture of the following i) and ii) wherein: i) is dichloromethane or trans-1,2-dichloroethylene; and ii) is 2,3-dihydrodecafluoropentane, 1,1,1,2,2,3,3,4,4,5,5,6,6-tridecafluorohexane, 1,1,1,2,2,2,3,3,4,4,5,5,6,6-dodecafluorohexane, or a hydrofluoroether.

[0006] Chinese patent publication number CN107073872B relates to a flame retardant thermal lining, which includes a non-woven sheet of nanofibers containing synthetic polymers, the non-woven sheet having a limiting oxygen index of at least 21, a mean flow pore of 10 microns or less, a thickness permeability of 25 to 6000 cubic feet per minute-microns (12 to 2880 cubic meters per square meters per minute-microns), and an average thickness T1; and a heat-stable flame-retardant fabric attached to the outer surface of the non-woven sheet, the fabric having an average thickness T2; the surface of the heat-stable fabric is in contact with the surface of the non-woven sheet; wherein T1 and T2 are selected so that the ratio of T1 to T2 is less than 0.75. The application relates to a flame-retardant composite fabric comprising the flame-retardant thermal lining and a garment comprising the flame-retardant composite fabric.

[0007] Chinese patent publication number CN109803818A relates to a packaging material including a sealed contact area with a nonwoven having an adhesive surface with an embossed pattern; a packaging material for providing a closed internal environment capable of sterilization, and a breathable fibrous nonwoven sheet structure useful in such a structure, wherein the nonwoven sheet structure has: at least one surface with a pre-sealed, embossed pattern; and a particle barrier penetration rate of less than 10%, a Glihill porosity of 40 seconds or less, and a moisture vapor transmission rate of 3500g / m2 / day or greater.

[0008] Chinese patent publication number CN109154138A relates to a composite material including a nonwoven vapor permeable sheet, a composite laminate comprising at least one water vapor permeable nonwoven sheet having a first and a second surface and a fluorinated polymer coating on the first surface of the sheet, wherein (i) the fluorinated polymer coating is present in an amount such that the total fluorine content of the coated nonwoven sheet is from 0.05 gsm to not more than 0.4 gsm, and (ii) the composite laminate exhibits a retained water pressure head of at least 60% when tested according to Test Method A after exposure to wet wood.

[0009] Chinese patent publication No. CN104159734B relates to a breathable product covering product for protecting bulk transportation and cold chain purposes, comprising a product to be protected and a protective covering sheet covering the product to be protected, wherein the covering sheet comprises at least one layer, the layer being made of a highly reflective moisture-permeable substrate having an outer side and an inner side, wherein the high reflectivity means reflecting more than 65% of visible light, the inner side being closest to the protected product, and at least one metal layer being adjacent to the inner side of the moisture-permeable substrate to provide controlled moisture vapor transmittance while achieving an appropriate emissivity through high reflection and low convection to provide thermal insulation, wherein the appropriate emissivity means an emissivity of less than 0.35.

[0010] Chinese patent publication number CN104969381B relates to a separator medium for an electrochemical cell, a separator medium for an electrochemical cell, the separator medium comprising at least one nonwoven sheet, the nonwoven sheet comprising polymer fibers, wherein the nonwoven sheet has a surface area of ​​0.5 to 1.5 m2 / g, a maximum pore size equal to or greater than 2.5 times the median flow pore size and greater than 11 times the minimum pore size, wherein the separator medium is obtained by a method comprising the following steps: spinning 12 wt% to 24 wt% polyethylene in a spinning agent at a spinning temperature of 205° C. to 220° C. The invention relates to a method for preparing a nonwoven web comprising: flash spinning a solution in a pre-spinning agent to form plexifilamentary fiber bundles, and collecting the plexifilamentary fiber bundles into an unbonded fiber web, wherein the spinning agent consists of a mixture of n-pentane and cyclopentane; unidirectionally stretching the unbonded fiber web in a longitudinal direction between heated stretching rollers at a temperature between 124° C. and 154° C. and positioned between 5 cm and 30 cm apart, and stretching the unbonded fiber web by between 3% and 25% to form a stretched fiber web; and bonding the stretched fiber web between heated bonding rollers at a temperature between 124° C. and 154° C. to form a nonwoven sheet, wherein the nonwoven sheet has a thickness of 0.5 to about 1.5 m 2 / g of surface area, and the method further includes sulfonating the nonwoven sheet after bonding the stretched fiber web.

[0011] Chinese Patent Publication No. CN105555528A Multilayer polymer sheet and lightweight laminate prepared therefrom A laminate comprising a multilayer polymer sheet and at least one additional layer; wherein the multilayer polymer sheet comprises two outer layers and comprises an inner layer, wherein the two outer layers are positioned on either side of the inner layer; wherein the inner layer comprises an ethylene-vinyl acetate composition; and wherein the two outer layers are the same or different and comprise an ionomer composition; the ionomer composition comprises an ionomer; and the ionomer is the product of a neutralized acid copolymer; wherein the acid copolymer comprises a copolymerized repeating unit derived from an olefin, about 0.1 wt % to about 30 wt % of a copolymerized repeating unit derived from a β-ethylenically unsaturated carboxylic acid having 3 to 8 carbon atoms, and optionally about 2 weight percent to about 25 weight percent of copolymerized repeat units derived from an ester of an ethylenically unsaturated carboxylic acid, the ester having from 4 to 12 carbon atoms; and the ethylenically unsaturated carboxylic acid and the ethylenically unsaturated carboxylic acid are the same or different; wherein the weight percents are based on the total weight of the acid copolymer, and the sum of the weight percents of the copolymerized residues in the acid copolymer is 100 weight percent; and wherein about 5% to about 100% of the carboxylic acid groups in the acid copolymer are neutralized with one or more bases containing a metal cation; and wherein the laminate has a sound transmission rating of greater than 25 as measured by ASTM E314; or wherein the laminate has an effective bending stiffness of about 3.0 mm to about 5.0 mm as measured by ASTM C158.

[0012] Chinese patent publication number CN103533996B relates to a method for preparing a liquid filter medium, comprising: flash spinning a solution of 12% to 24% by weight of polyethylene in a spinning agent at a spinning temperature of 205°C to 220°C to form plexifilamentary fiber bundles, the spinning agent consisting of a mixture of n-pentane and cyclopentane, and collecting the plexifilamentary fiber bundles into an unbonded fiber web; at a temperature between 124°C and 154°C, uniaxially stretching the unbonded fiber web in the longitudinal direction between heated stretching rollers positioned between 5 cm and 30 cm apart, and stretching by 3% to 25% to form a stretched fiber web; and bonding the stretched fiber web between heated bonding rollers at a temperature between 124°C and 154°C to form a nonwoven sheet, wherein the nonwoven sheet has a water flow rate of at least 10 ml / min / cm2 / KPa and a bending filtration coefficient of at least 3.0, and wherein the nonwoven sheet is a nonwoven sheet stretched uniaxially in the longitudinal direction. [Summary of the invention]

[0013] The purpose of the present invention is to overcome the shortcomings of the prior art and provide a printable polymer sheet and its application.

[0014] The objective of the present invention is achieved through the following technical solutions:

[0015] A printable polymer sheet, the raw material of which is mainly polyethylene, with a gram weight of 46 to 76 g / m 2 ;

[0016] The positive printing surface strength is greater than 3.4m / s;

[0017] The reverse printing surface strength is greater than 2.8m / s;

[0018] Smoothness is 25 to 50 seconds;

[0019] Burst resistance index is 6~12kPa·m 2 / g.

[0020] The positive printing surface strength of the polymer sheet is 3.4-4.4 m / s or 4.4-5.4 m / s or 5.4-6.4 m / s.

[0021] The reverse printing surface strength of the polymer sheet is 2.8 to 3.8 m / s or 3.8 to 4.8 m / s or 4.8 to 5.8 m / s.

[0022] The polymer sheet has a smoothness of 25 to 35 seconds, or 35 to 42 seconds, or 42 to 50 seconds.

[0023] The bursting index of polymer sheet is 6~8kPa·m 2 / g or 8~10kPa·m 2 / g or 10~12kPa·m 2 / g.

[0024] The invention discloses a printable polymer sheet, the raw material of which further comprises modified polybutylene terephthalate powder.

[0025] The modified polybutylene terephthalate is modified polybutylene terephthalate doped with antimony white.

[0026] The mass fraction of the modified polybutylene terephthalate in the polymer sheet is 1.5-3%.

[0027] A method for preparing a printable polymer sheet, comprising the following technical steps:

[0028] The spinning solution is flash-spun, and then the flash-spun fiber is passed through a web laying process, and then through a hot roller heat pressing molding and calendering process to obtain a polymer sheet;

[0029] The spinning solution comprises modified polybutylene terephthalate and polyethylene, and a spinning solvent.

[0030] The preferred technical solutions are as follows:

[0031] A method for preparing a printable polymer sheet, comprising the following technical steps:

[0032] Step 1: (1) Dispersing antimony white powder and aluminum chloride powder in an alkaline potassium hydroxide solution, then stirring at high speed and ultrasonically dispersing, separating the precipitate, filtering and drying, and calcining to obtain an antimony white powder surface adsorbed aluminum oxide composite material; (2) Stirring at high speed and ultrasonically dispersing the antimony white powder surface adsorbed aluminum oxide composite material in an n-pentane solution, and then adding 3-aminopropyltriethoxysilane to react; after the reaction is completed, centrifugation is performed, and the solid is vacuum dried to prepare an antimony white modified composite material with adsorption functional groups; (3) Then, monobutyl maleate, initiator diisopropyl peroxide, antimony white modified composite material and PBT are coarsely ground and finely ground, and then melt-extruded and granulated by an extruder to obtain modified polybutylene terephthalate doped with antimony white.

[0033] The mass ratio of antimony white powder to aluminum chloride powder is 2:1 to 4:1.

[0034] The mass fraction of antimony white powder in the potassium hydroxide alkaline solution is 5-10%, and the alkaline solution is kept in excess.

[0035] The mass concentration of the alumina composite material adsorbed on the surface of antimony white powder in n-pentane is 15-50 g / L.

[0036] The 3-aminopropyltriethoxysilane is 2-5% by weight of the alumina composite material adsorbed on the surface of the antimony white powder, preferably 4%.

[0037] The mass fraction of monobutyl maleate in the modified polybutylene terephthalate doped with antimony white is 0.5-2%.

[0038] The mass fraction of the initiator dicumyl peroxide in the modified polybutylene terephthalate doped with antimony white is 0.1-1%.

[0039] The mass fraction of the antimony white modified composite material in the modified polybutylene terephthalate doped with antimony white is 2-5%.

[0040] Monobutyl maleate, antimony white modified composite material and PBT are firstly coarsely ground and finely ground, and then extruded and granulated by an extruder to obtain modified polybutylene terephthalate powder doped with antimony white. In this process, the grafting rate is 1.5-2%.

[0041] High-speed stirring process: stirring speed is 1500-2500 rpm, stirring time is 0.5-2 hours.

[0042] Ultrasonic dispersion process: The dispersion time is 2 to 3 hours.

[0043] Calcination process: The calcination heating rate is 10°C / min, and the temperature is increased to 450°C.

[0044] Rough grinding process: grinding speed is 500-750rpm, and grinding time is 0.5-1 hour.

[0045] Fine grinding process: grinding speed is 1500-2500rpm, and grinding time is 1-2 hours.

[0046] The present application forms precipitated aluminum hydroxide on the surface of antimony white powder first, and then generates alumina through a calcination process, that is, a protective layer of alumina is wrapped around the antimony white powder, which has a longer-lasting and sustained-release whitening effect than directly adding antimony white powder to the flash sheet (such as the poor performance test data of comparative example 1). At the same time, due to the addition of inorganic matter (alumina composite material adsorbed on the surface of antimony white powder), it enters the fiber gaps of the flash sheet, increases its smoothness and improves printability (such as the poor performance test data of comparative example 2); at the same time, by adsorbing alumina composite material on the surface of antimony white powder, first grafting of hydroxyl groups (using the multi-hydroxyl characteristics of n-pentane solution) and then adding amino group grafting (using the amino group of 3-aminopropyltriethoxysilane); the surface of the inorganic matter (alumina composite material adsorbed on the surface of antimony white powder) is grouped, which is beneficial to the grafting reaction in the subsequent melt extrusion process (such as the poor performance test data of comparative example 3). The present application adds a coarse grinding and fine grinding process before the melt extrusion process step, and uses a dry powder ball mill; various raw materials can be ground so that the raw materials are fully contacted and dispersed, avoiding the difficulty of dispersion during extrusion, allowing various components to be mixed with each other, improving surface activity, and making the material dispersion more uniform, which is beneficial to the dispersibility of the final product of melt extrusion (such as the poor performance test data of Comparative Example 4). The present application can reduce the interfacial tension with the polyethylene matrix in the future flash spinning process due to the grafted alkyl chain polar monomer in the PBT particles, improve the compatibility of the modified polybutylene terephthalate doped with antimony white and the polyethylene monomer, and is beneficial to the flash spinning process, which is also one of the factors for us to choose this material. However, when the content of the modified polybutylene terephthalate doped with antimony white reaches a certain level in the sheet, its effect on promoting dispersion and interfacial bonding of polyethylene is no longer obvious, that is, with the increase of the amount added, it no longer plays a role in improving the performance (such as the poor performance test data of Comparative Examples 8-11). The present application utilizes the addition of inorganic substances to improve the printability of the sheet, and utilizes the high toughness of PBT itself to improve the technical problem of poor printability caused by insufficient toughness of polyethylene sheets.

[0047] Step 2: dissolving the modified polybutylene terephthalate doped with antimony white prepared in step 1 and polyethylene particles in a spinning solvent, controlling the pressure of the spinning solution to be 40 to 80 bar, to obtain a spinning solution;

[0048] The mass fraction of modified polybutylene terephthalate doped with antimony white and polyethylene particles in the spinning solution is 10-13%; when the mass fraction of the raw materials in the spinning solution is too high or too low, it will have a significant impact on the final performance of the product (such as the poor performance test data of comparative examples 5-7).

[0049] The mass fraction of the modified polybutylene terephthalate in the mixture of the modified polybutylene terephthalate doped with antimony white and the polyethylene particles is 1.5-3%.

[0050] The spinning solvent is selected from one or a mixture of two or more of aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, unsaturated hydrocarbons, halogenated hydrocarbons, esters, ethers, and fluorocarbons.

[0051] The spinning solvent is preferably 1,2-dichloroethylene, 2,3-dihydrodecafluoropentane, and 1,1,1,2-tetrafluoro-2-chloroethane, and the volume ratio of the three is 6:2:2.

[0052] Step three: flash-spin the spinning solution prepared in step two, and then pass the flash-spun fiber through a web laying procedure, and then through a hot roller heat pressing and calendering process to obtain a polymer sheet; wherein the spinning temperature is 200-220°C, and the spinning pressure is 40-80 bar.

[0053] The invention discloses an application of a printable polymer sheet in printing packaging materials.

[0054] The polymer sheet prepared by flash evaporation has excellent waterproof and breathable properties, isolating chemical liquids, dry and wet particles, and its physical properties are not affected by immersion in water. Therefore, it can be used as various high-grade papers such as book paper, map paper, and currency paper, such as field maps, military charts, outdoor posters, flags, etc. It is not afraid of wind and rain, and is an ideal material for use in harsh environments.

[0055] Compared with the prior art, the present invention has the following positive effects:

[0056] The present application utilizes the addition of inorganic substances to improve the printability of the sheet, and utilizes the high toughness of PBT itself to improve the technical problem of poor printability caused by insufficient toughness of polyethylene. [Specific implementation method]

[0057] The following provides specific embodiments of a printable polymer sheet and its application according to the present invention.

[0058] Specific test method for the samples prepared in this application:

[0059] 1. Printing surface strength:

[0060] The printing surface intensity is the speed at which the material surface is printed at a continuously increasing speed until the material surface begins to fuzz, expressed in m / s.

[0061] The test of printed surface strength is shown in the national standard GB / T 22365-2008.

[0062] Here, it is defined as follows: testing the front side of the sample to obtain the positive printed surface strength, and then testing the other side of the sample to obtain the reverse printed surface strength.

[0063] The higher the printing surface strength, the better for printing. However, if the printing surface strength is too high, the product will be soft and the strength of the product will be too low.

[0064] 2. Smoothness:

[0065] Smoothness: The time required for a certain amount of air to leak from the atmosphere between the sample surface and the annular plate surface under a specific contact state and a certain pressure difference, measured in seconds.

[0066] The test of smoothness is based on the national standard GB / T 456-2002, Determination of smoothness of paper and paperboard (Buick method). Take 10 samples, test the smoothness of the front and back of each sample respectively, and then average them to obtain the smoothness of the sample.

[0067] When the smoothness is high, the tightness increases, which leads to a decrease in the ink absorption performance, so the smoothness should not be too high. When the smoothness is low, it is relatively soft and the strength of the product is too low. Combined with other performance parameters, this application selects a smoothness range of 25 to 50s to give the product a better printing effect.

[0068] 3. Burst resistance index:

[0069] The bursting index is the bursting strength divided by the quantitative value; the bursting strength refers to the maximum pressure when the elastic film breaks the circular area of ​​the paper sample under the pressure applied by the hydraulic system.

[0070] The test standard of bursting index refers to the national standard GB / T 1539-2007 / ISO 2759:2001, IDT. Sampling is carried out according to the requirements of the standard. The samples are first subjected to temperature and humidity price treatment. The process conditions of temperature and humidity treatment are: temperature 22-24℃, humidity 48-52%RH, time 4 hours, temperature and humidity air conditioning unit. The samples after temperature and humidity treatment are tested under the following test conditions: test environment temperature 22-24℃, test environment humidity 48-52%RH.

[0071] For the tear resistance index, the larger the better. Therefore, it is necessary to find a dynamic balance between the tear resistance index, surface printing strength, smoothness and D65 brightness performance parameters, that is, it has a certain tear resistance index under the premise of having a good printing effect.

[0072] 4. D65 brightness:

[0073] The test of D65 brightness refers to the national standard GB / T 7974-2013, which follows the test method for paper and paperboard, in which the front and back sides of the sample are tested separately, and then the average is calculated to obtain the D65 brightness.

[0074] For thin sheet materials, especially when used as outdoor packaging materials, they must have very high brightness due to printing requirements. Relatively speaking, the higher the brightness, the better, so as to resist the technical problem of yellowing caused by aging of the thin sheet material itself.

[0075] Example 1

[0076] A method for preparing a printable polymer sheet, comprising the following technical steps:

[0077] Step 1: (1) Dispersing antimony white powder and aluminum chloride powder in an alkaline potassium hydroxide solution, then stirring at high speed and ultrasonically dispersing, separating the precipitate, filtering and drying, and calcining to obtain an antimony white powder surface adsorbed aluminum oxide composite material; (2) Stirring at high speed and ultrasonically dispersing the antimony white powder surface adsorbed aluminum oxide composite material in an n-pentane solution, and then adding 3-aminopropyltriethoxysilane to react; after the reaction is completed, centrifugation is performed, and the solid is vacuum dried to prepare an antimony white modified composite material with adsorption functional groups; (3) Then, monobutyl maleate, initiator diisopropyl peroxide, antimony white modified composite material and PBT are coarsely ground and finely ground, and then melt-extruded and granulated by an extruder to obtain modified polybutylene terephthalate doped with antimony white.

[0078] The mass ratio of antimony white powder to aluminum chloride powder is 2:1.

[0079] The mass fraction of antimony white powder in the potassium hydroxide alkaline solution is 5%, and the alkaline solution is kept in excess.

[0080] The mass concentration of alumina composite material adsorbed on the surface of antimony white powder in n-pentane is 21 g / L.

[0081] The mass of 3-aminopropyltriethoxysilane is 2.2.5% of the alumina composite material adsorbed on the surface of antimony white powder.

[0082] The mass fraction of monobutyl maleate in the modified polybutylene terephthalate doped with antimony white is 0.5%.

[0083] The mass fraction of the initiator dicumyl peroxide in the modified polybutylene terephthalate doped with antimony white is 0.2%.

[0084] The mass fraction of the antimony white modified composite material in the antimony white-doped modified polybutylene terephthalate is 2%.

[0085] Monobutyl maleate, antimony white modified composite material and PBT are firstly coarsely ground and finely ground, and then extruded and granulated by an extruder to obtain modified polybutylene terephthalate powder doped with antimony white. In this process, the grafting rate is 1.5%.

[0086] High-speed stirring process: stirring speed is 1500 rpm, stirring time is 1 hour.

[0087] Ultrasonic dispersion process: dispersion time is 2 hours.

[0088] Calcination process: The calcination heating rate is 10°C / min, and the temperature is increased to 450°C.

[0089] Coarse grinding process: grinding speed is 550 rpm, grinding time is 0.5 hour.

[0090] Fine grinding process: grinding speed is 1600 rpm, grinding time is 1 hour.

[0091] Step 2: dissolving the modified polybutylene terephthalate doped with antimony white prepared in step 1 and polyethylene particles in a spinning solvent, controlling the pressure of the spinning solution to be 40 to 50 bar, to obtain a spinning solution;

[0092] The mass fraction of modified polybutylene terephthalate doped with antimony white and polyethylene particles in the spinning solution is 10.5%;

[0093] The mass fraction of the modified polybutylene terephthalate in the mixture of the modified polybutylene terephthalate doped with antimony white and the polyethylene particles is 1.5%.

[0094] The spinning solvent is 1,2-dichloroethylene, 2,3-dihydrodecafluoropentane, and 1,1,1,2-tetrafluoro-2-chloroethane, and the volume ratio of the three is 6:2:2.

[0095] Step 3: flash spinning the spinning solution prepared in step 2, and then pass the flash fiber through a web laying process, and then through a hot roller hot pressing molding and calendering process to obtain a polymer sheet; wherein the spinning temperature is 200-220°C and the spinning pressure is 40-50 bar. The performance test method is described above, and the test data results are shown in Table 1.

[0096] Example 2

[0097] A method for preparing a printable polymer sheet, comprising the following technical steps:

[0098] Step 1: (1) Dispersing antimony white powder and aluminum chloride powder in an alkaline potassium hydroxide solution, then stirring at high speed and ultrasonically dispersing, separating the precipitate, filtering and drying, and calcining to obtain an antimony white powder surface adsorbed aluminum oxide composite material; (2) Stirring at high speed and ultrasonically dispersing the antimony white powder surface adsorbed aluminum oxide composite material in an n-pentane solution, and then adding 3-aminopropyltriethoxysilane to react; after the reaction is completed, centrifugation is performed, and the solid is vacuum dried to prepare an antimony white modified composite material with adsorption functional groups; (3) Then, monobutyl maleate, initiator diisopropyl peroxide, antimony white modified composite material and PBT are coarsely ground and finely ground, and then melt-extruded and granulated by an extruder to obtain modified polybutylene terephthalate doped with antimony white.

[0099] The mass ratio of antimony white powder to aluminum chloride powder is 3:1.

[0100] The mass fraction of antimony white powder in the potassium hydroxide alkaline solution is 7%, and the alkaline solution is kept in excess.

[0101] The mass concentration of alumina composite material adsorbed on the surface of antimony white powder in n-pentane is 27g / L.

[0102] The 3-aminopropyltriethoxysilane is 4% by weight of the alumina composite material adsorbed on the surface of the antimony white powder.

[0103] The mass fraction of monobutyl maleate in the modified polybutylene terephthalate doped with antimony white is 1%.

[0104] The mass fraction of the initiator dicumyl peroxide in the modified polybutylene terephthalate doped with antimony white is 0.6%.

[0105] The mass fraction of the antimony white modified composite material in the antimony white-doped modified polybutylene terephthalate is 4%.

[0106] Monobutyl maleate, antimony white modified composite material and PBT are firstly coarsely ground and finely ground, and then extruded and granulated by an extruder to obtain modified polybutylene terephthalate powder doped with antimony white. In this process, the grafting rate is 1.7%.

[0107] High-speed stirring process: stirring speed is 2100 rpm, stirring time is 1 hour.

[0108] Ultrasonic dispersion process: dispersion time is 2.5 hours.

[0109] Calcination process: The calcination heating rate is 10°C / min, and the temperature is increased to 450°C.

[0110] Coarse grinding process: grinding speed is 650 rpm, and grinding time is 1 hour.

[0111] Fine grinding process: grinding speed is 2200rpm, grinding time is 2 hours.

[0112] Step 2: dissolving the modified polybutylene terephthalate doped with antimony white prepared in step 1 and polyethylene particles in a spinning solvent, controlling the pressure of the spinning solution to be 50-60 bar, to obtain a spinning solution;

[0113] The mass fraction of modified polybutylene terephthalate doped with antimony white and polyethylene particles in the spinning solution is 11.5%;

[0114] The mass fraction of the modified polybutylene terephthalate in the mixture of the modified polybutylene terephthalate doped with antimony white and the polyethylene particles is 2%.

[0115] The spinning solvent is 1,2-dichloroethylene, 2,3-dihydrodecafluoropentane, and 1,1,1,2-tetrafluoro-2-chloroethane, and the volume ratio of the three is 6:2:2.

[0116] Step 3: flash spinning the spinning solution prepared in step 2, and then pass the flash fiber through a web laying process, and then through a hot roller hot pressing molding and calendering process to obtain a polymer sheet; wherein the spinning temperature is 200-220°C and the spinning pressure is 50-60 bar. The performance test method is described above, and the test data results are shown in Table 1.

[0117] Example 3

[0118] A method for preparing a printable polymer sheet, comprising the following technical steps:

[0119] Step 1: (1) Dispersing antimony white powder and aluminum chloride powder in an alkaline potassium hydroxide solution, then stirring at high speed and ultrasonically dispersing, separating the precipitate, filtering and drying, and calcining to obtain an antimony white powder surface adsorbed aluminum oxide composite material; (2) Stirring at high speed and ultrasonically dispersing the antimony white powder surface adsorbed aluminum oxide composite material in an n-pentane solution, and then adding 3-aminopropyltriethoxysilane to react; after the reaction is completed, centrifugation is performed, and the solid is vacuum dried to prepare an antimony white modified composite material with adsorption functional groups; (3) Then, monobutyl maleate, initiator diisopropyl peroxide, antimony white modified composite material and PBT are coarsely ground and finely ground, and then melt-extruded and granulated by an extruder to obtain modified polybutylene terephthalate doped with antimony white.

[0120] The mass ratio of antimony white powder to aluminum chloride powder is 4:1.

[0121] The mass fraction of antimony white powder in the potassium hydroxide alkaline solution is 10%, and the alkaline solution is kept in excess.

[0122] The mass concentration of the alumina composite material adsorbed on the surface of antimony white powder in n-pentane is 45 g / L.

[0123] The 3-aminopropyltriethoxysilane is 5% by weight of the alumina composite material adsorbed on the surface of the antimony white powder.

[0124] The mass fraction of monobutyl maleate in the modified polybutylene terephthalate doped with antimony white is 2%.

[0125] The mass fraction of the initiator dicumyl peroxide in the modified polybutylene terephthalate doped with antimony white is 0.8%.

[0126] The mass fraction of the antimony white modified composite material in the antimony white-doped modified polybutylene terephthalate is 5%.

[0127] Monobutyl maleate, antimony white modified composite material and PBT are firstly coarsely ground and finely ground, and then extruded and granulated by an extruder to obtain modified polybutylene terephthalate powder doped with antimony white. In this process, the grafting rate is 2%.

[0128] High-speed stirring process: stirring speed is 2500 rpm and stirring time is 2 hours.

[0129] Ultrasonic dispersion process: dispersion time is 3 hours.

[0130] Calcination process: The calcination heating rate is 10°C / min, and the temperature is increased to 450°C.

[0131] Coarse grinding process: grinding speed is 750 rpm, and grinding time is 1 hour.

[0132] Fine grinding process: grinding speed is 2500rpm, grinding time is 2 hours.

[0133] Step 2: dissolving the modified polybutylene terephthalate doped with antimony white prepared in step 1 and polyethylene particles in a spinning solvent, controlling the pressure of the spinning solution to be 60-70 bar, to obtain a spinning solution;

[0134] The mass fraction of modified polybutylene terephthalate doped with antimony white and polyethylene particles in the spinning solution is 12.5%;

[0135] The mass fraction of the modified polybutylene terephthalate in the mixture of the modified polybutylene terephthalate doped with antimony white and the polyethylene particles is 3%.

[0136] The spinning solvent is 1,2-dichloroethylene, 2,3-dihydrodecafluoropentane, and 1,1,1,2-tetrafluoro-2-chloroethane, and the volume ratio of the three is 6:2:2.

[0137] Step 3: flash spinning the spinning solution prepared in step 2, and then pass the flash fiber through a web laying process, and then through a hot roller hot pressing molding and calendering process to obtain a polymer sheet; wherein the spinning temperature is 200-220°C and the spinning pressure is 60-70 bar. The performance test method is described above, and the test data results are shown in Table 1.

[0138] Comparative Example 1

[0139] A method for preparing a printable polymer sheet, comprising the following technical steps:

[0140] Step 1: (1) Antimony white powder, aluminum oxide, monobutyl maleate, initiator diisopropylbenzene peroxide, antimony white modified composite material and PBT are mixed, and then melt-extruded and granulated by an extruder to obtain modified polybutylene terephthalate doped with antimony white.

[0141] The mass fraction of antimony white powder in the modified polybutylene terephthalate doped with antimony white is 3%;

[0142] The mass fraction of aluminum oxide in the modified polybutylene terephthalate doped with antimony white is 1%;

[0143] The mass fraction of monobutyl maleate in the modified polybutylene terephthalate doped with antimony white is 1%.

[0144] The mass fraction of the initiator dicumyl peroxide in the modified polybutylene terephthalate doped with antimony white is 0.6%.

[0145] The mass fraction of the antimony white modified composite material in the antimony white-doped modified polybutylene terephthalate is 4%.

[0146] Step 2: dissolving the modified polybutylene terephthalate doped with antimony white prepared in step 1 and polyethylene particles in a spinning solvent, controlling the pressure of the spinning solution to be 50-60 bar, to obtain a spinning solution;

[0147] The mass fraction of modified polybutylene terephthalate doped with antimony white and polyethylene particles in the spinning solution is 11.5%;

[0148] The mass fraction of the modified polybutylene terephthalate in the mixture of the modified polybutylene terephthalate doped with antimony white and the polyethylene particles is 2%.

[0149] The spinning solvent is 1,2-dichloroethylene, 2,3-dihydrodecafluoropentane, and 1,1,1,2-tetrafluoro-2-chloroethane, and the volume ratio of the three is 6:2:2.

[0150] Step 3: flash spinning the spinning solution prepared in step 2, and then pass the flash fiber through a web laying process, and then through a hot roller hot pressing molding and calendering process to obtain a polymer sheet; wherein the spinning temperature is 200-220°C and the spinning pressure is 50-60 bar. The performance test method is described above, and the test data results are shown in Table 1.

[0151] Comparative Example 2

[0152] A method for preparing a printable polymer sheet, comprising the following technical steps:

[0153] Step 1: (1) stirring antimony white powder in an n-pentane solution at high speed and dispersing it by ultrasonication, and then adding 3-aminopropyltriethoxysilane to react; after the reaction is completed, centrifugation is performed, and the solid is vacuum dried to prepare an antimony white modified composite material with adsorption functional groups; (2) monobutyl maleate, initiator diisopropyl peroxide, antimony white modified composite material and PBT are first coarsely ground and finely ground, and then melt-extruded and granulated by an extruder to obtain modified polybutylene terephthalate doped with antimony white.

[0154] The mass concentration of antimony white powder in n-pentane is 27 g / L.

[0155] The content of 3-aminopropyltriethoxysilane is 4% by mass of the antimony white powder.

[0156] The mass fraction of monobutyl maleate in the modified polybutylene terephthalate doped with antimony white is 1%.

[0157] The mass fraction of the initiator dicumyl peroxide in the modified polybutylene terephthalate doped with antimony white is 0.6%.

[0158] The mass fraction of the antimony white modified composite material in the antimony white-doped modified polybutylene terephthalate is 4%.

[0159] Monobutyl maleate, antimony white modified composite material and PBT are firstly coarsely ground and finely ground, and then extruded and granulated by an extruder to obtain modified polybutylene terephthalate powder doped with antimony white. In this process, the grafting rate is 1.7%.

[0160] Coarse grinding process: grinding speed is 650 rpm, and grinding time is 1 hour.

[0161] Fine grinding process: grinding speed is 2200rpm, grinding time is 2 hours.

[0162] Step 2: dissolving the modified polybutylene terephthalate doped with antimony white prepared in step 1 and polyethylene particles in a spinning solvent, controlling the pressure of the spinning solution to be 50-60 bar, to obtain a spinning solution;

[0163] The mass fraction of modified polybutylene terephthalate doped with antimony white and polyethylene particles in the spinning solution is 11.5%;

[0164] The mass fraction of the modified polybutylene terephthalate in the mixture of the modified polybutylene terephthalate doped with antimony white and the polyethylene particles is 2%.

[0165] The spinning solvent is 1,2-dichloroethylene, 2,3-dihydrodecafluoropentane, and 1,1,1,2-tetrafluoro-2-chloroethane, and the volume ratio of the three is 6:2:2.

[0166] Step 3: flash spinning the spinning solution prepared in step 2, and then pass the flash fiber through a web laying process, and then through a hot roller hot pressing molding and calendering process to obtain a polymer sheet; wherein the spinning temperature is 200-220°C and the spinning pressure is 50-60 bar. The performance test method is described above, and the test data results are shown in Table 1.

[0167] Comparative Example 3

[0168] A method for preparing a printable polymer sheet, comprising the following technical steps:

[0169] Step 1: (1) dispersing antimony white powder and aluminum chloride powder in an alkaline potassium hydroxide solution, and then stirring at a high speed and ultrasonically dispersing, separating the precipitate, filtering and drying, and calcining to obtain an antimony white powder surface adsorbed aluminum oxide composite material; (2) then coarsely grinding and finely grinding monobutyl maleate, initiator diisopropylbenzene peroxide, the antimony white powder surface adsorbed aluminum oxide composite material and PBT, and then melt-extruding and granulating them through an extruder to obtain modified polybutylene terephthalate doped with antimony white.

[0170] The mass ratio of antimony white powder to aluminum chloride powder is 3:1.

[0171] The mass fraction of antimony white powder in the potassium hydroxide alkaline solution is 7%, and the alkaline solution is kept in excess.

[0172] The mass fraction of monobutyl maleate in the modified polybutylene terephthalate doped with antimony white is 1%.

[0173] The mass fraction of the initiator dicumyl peroxide in the modified polybutylene terephthalate doped with antimony white is 0.6%.

[0174] The mass fraction of the aluminum oxide composite material adsorbed on the surface of the white powder in the modified polybutylene terephthalate doped with antimony white is 4%.

[0175] Monobutyl maleate, antimony white modified composite material and PBT are firstly coarsely ground and finely ground, and then extruded and granulated by an extruder to obtain modified polybutylene terephthalate powder doped with antimony white. In this process, the grafting rate is 1.7%.

[0176] High-speed stirring process: stirring speed is 2100 rpm, stirring time is 1 hour.

[0177] Ultrasonic dispersion process: dispersion time is 2.5 hours.

[0178] Calcination process: The calcination heating rate is 10°C / min, and the temperature is increased to 450°C.

[0179] Coarse grinding process: grinding speed is 650 rpm, and grinding time is 1 hour.

[0180] Fine grinding process: grinding speed is 2200rpm, grinding time is 2 hours.

[0181] Step 2: dissolving the modified polybutylene terephthalate doped with antimony white prepared in step 1 and polyethylene particles in a spinning solvent, controlling the pressure of the spinning solution to be 50-60 bar, to obtain a spinning solution;

[0182] The mass fraction of modified polybutylene terephthalate doped with antimony white and polyethylene particles in the spinning solution is 11.5%;

[0183] The mass fraction of the modified polybutylene terephthalate in the mixture of the modified polybutylene terephthalate doped with antimony white and the polyethylene particles is 2%.

[0184] The spinning solvent is 1,2-dichloroethylene, 2,3-dihydrodecafluoropentane, and 1,1,1,2-tetrafluoro-2-chloroethane, and the volume ratio of the three is 6:2:2.

[0185] Step 3: flash spinning the spinning solution prepared in step 2, and then pass the flash fiber through a web laying process, and then through a hot roller hot pressing molding and calendering process to obtain a polymer sheet; wherein the spinning temperature is 200-220°C and the spinning pressure is 50-60 bar. The performance test method is described above, and the test data results are shown in Table 1.

[0186] Comparative Example 4

[0187] A method for preparing a printable polymer sheet, comprising the following technical steps:

[0188] Step 1: (1) dispersing antimony white powder and aluminum chloride powder in an alkaline potassium hydroxide solution, and then stirring at high speed and ultrasonically dispersing, separating the precipitate, filtering and drying, and calcining to obtain an antimony white powder surface adsorbed aluminum oxide composite material; (2) stirring at high speed and ultrasonically dispersing the antimony white powder surface adsorbed aluminum oxide composite material in an n-pentane solution, and then adding 3-aminopropyltriethoxysilane to react; after the reaction is completed, centrifugation is performed, and the solid is vacuum dried to prepare an antimony white modified composite material with adsorption functional groups; (3) then mixing the initiator diisopropyl peroxide, the antimony white modified composite material and PBT, and passing through an extruder for melt extrusion granulation to obtain antimony white doped modified polybutylene terephthalate.

[0189] The mass ratio of antimony white powder to aluminum chloride powder is 3:1.

[0190] The mass fraction of antimony white powder in the potassium hydroxide alkaline solution is 7%, and the alkaline solution is kept in excess.

[0191] The mass concentration of alumina composite material adsorbed on the surface of antimony white powder in n-pentane is 27g / L.

[0192] The 3-aminopropyltriethoxysilane is 4% by weight of the alumina composite material adsorbed on the surface of the antimony white powder.

[0193] The mass fraction of the initiator dicumyl peroxide in the modified polybutylene terephthalate doped with antimony white is 0.6%.

[0194] The mass fraction of the antimony white modified composite material in the antimony white-doped modified polybutylene terephthalate is 4%.

[0195] Monobutyl maleate, antimony white modified composite material and PBT are firstly coarsely ground and finely ground, and then extruded and granulated by an extruder to obtain modified polybutylene terephthalate powder doped with antimony white. In this process, the grafting rate is 1.7%.

[0196] High-speed stirring process: stirring speed is 2100 rpm, stirring time is 1 hour.

[0197] Ultrasonic dispersion process: dispersion time is 2.5 hours.

[0198] Calcination process: The calcination heating rate is 10°C / min, and the temperature is increased to 450°C.

[0199] Step 2: dissolving the modified polybutylene terephthalate doped with antimony white prepared in step 1 and polyethylene particles in a spinning solvent, controlling the pressure of the spinning solution to be 50-60 bar, to obtain a spinning solution;

[0200] The mass fraction of modified polybutylene terephthalate doped with antimony white and polyethylene particles in the spinning solution is 11.5%;

[0201] The mass fraction of the modified polybutylene terephthalate in the mixture of the modified polybutylene terephthalate doped with antimony white and the polyethylene particles is 2%.

[0202] The spinning solvent is 1,2-dichloroethylene, 2,3-dihydrodecafluoropentane, and 1,1,1,2-tetrafluoro-2-chloroethane, and the volume ratio of the three is 6:2:2.

[0203] Step 3: flash spinning the spinning solution prepared in step 2, and then pass the flash fiber through a web laying process, and then through a hot roller hot pressing molding and calendering process to obtain a polymer sheet; wherein the spinning temperature is 200-220°C and the spinning pressure is 50-60 bar. The performance test method is described above, and the test data results are shown in Table 1.

[0204] Comparative Example 5

[0205] A method for preparing a printable polymer sheet, comprising the following technical steps:

[0206] Step 1: (1) Dispersing antimony white powder and aluminum chloride powder in an alkaline potassium hydroxide solution, then stirring at high speed and ultrasonically dispersing, separating the precipitate, filtering and drying, and calcining to obtain an antimony white powder surface adsorbed aluminum oxide composite material; (2) Stirring at high speed and ultrasonically dispersing the antimony white powder surface adsorbed aluminum oxide composite material in an n-pentane solution, and then adding 3-aminopropyltriethoxysilane to react; after the reaction is completed, centrifugation is performed, and the solid is vacuum dried to prepare an antimony white modified composite material with adsorption functional groups; (3) Then, monobutyl maleate, initiator diisopropyl peroxide, antimony white modified composite material and PBT are coarsely ground and finely ground, and then melt-extruded and granulated by an extruder to obtain modified polybutylene terephthalate doped with antimony white.

[0207] The mass ratio of antimony white powder to aluminum chloride powder is 3:1.

[0208] The mass fraction of antimony white powder in the potassium hydroxide alkaline solution is 7%, and the alkaline solution is kept in excess.

[0209] The mass concentration of alumina composite material adsorbed on the surface of antimony white powder in n-pentane is 27g / L.

[0210] The 3-aminopropyltriethoxysilane is 4% by weight of the alumina composite material adsorbed on the surface of the antimony white powder.

[0211] The mass fraction of monobutyl maleate in the modified polybutylene terephthalate doped with antimony white is 1%.

[0212] The mass fraction of the initiator dicumyl peroxide in the modified polybutylene terephthalate doped with antimony white is 0.6%.

[0213] The mass fraction of the antimony white modified composite material in the antimony white-doped modified polybutylene terephthalate is 4%.

[0214] Monobutyl maleate, antimony white modified composite material and PBT are firstly coarsely ground and finely ground, and then extruded and granulated by an extruder to obtain modified polybutylene terephthalate powder doped with antimony white. In this process, the grafting rate is 1.7%.

[0215] High-speed stirring process: stirring speed is 2100 rpm, stirring time is 1 hour.

[0216] Ultrasonic dispersion process: dispersion time is 2.5 hours.

[0217] Calcination process: The calcination heating rate is 10°C / min, and the temperature is increased to 450°C.

[0218] Coarse grinding process: grinding speed is 650 rpm, and grinding time is 1 hour.

[0219] Fine grinding process: grinding speed is 2200rpm, grinding time is 2 hours.

[0220] Step 2: dissolving the modified polybutylene terephthalate doped with antimony white prepared in step 1 and polyethylene particles in a spinning solvent, controlling the pressure of the spinning solution to be 50-60 bar, to obtain a spinning solution;

[0221] The mass fraction of modified polybutylene terephthalate doped with antimony white and polyethylene particles in the spinning solution is 9.5%

[0222] The mass fraction of the modified polybutylene terephthalate in the mixture of the modified polybutylene terephthalate doped with antimony white and the polyethylene particles is 2%.

[0223] The spinning solvent is 1,2-dichloroethylene, 2,3-dihydrodecafluoropentane, and 1,1,1,2-tetrafluoro-2-chloroethane, and the volume ratio of the three is 6:2:2.

[0224] Step 3: flash spinning the spinning solution prepared in step 2, and then pass the flash fiber through a web laying process, and then through a hot roller hot pressing molding and calendering process to obtain a polymer sheet; wherein the spinning temperature is 200-220°C and the spinning pressure is 50-60 bar. The performance test method is described above, and the test data results are shown in Table 1.

[0225] Comparative Example 6

[0226] A method for preparing a printable polymer sheet, comprising the following technical steps:

[0227] Step 1: (1) Dispersing antimony white powder and aluminum chloride powder in an alkaline potassium hydroxide solution, then stirring at high speed and ultrasonically dispersing, separating the precipitate, filtering and drying, and calcining to obtain an antimony white powder surface adsorbed aluminum oxide composite material; (2) Stirring at high speed and ultrasonically dispersing the antimony white powder surface adsorbed aluminum oxide composite material in an n-pentane solution, and then adding 3-aminopropyltriethoxysilane to react; after the reaction is completed, centrifugation is performed, and the solid is vacuum dried to prepare an antimony white modified composite material with adsorption functional groups; (3) Then, monobutyl maleate, initiator diisopropyl peroxide, antimony white modified composite material and PBT are coarsely ground and finely ground, and then melt-extruded and granulated by an extruder to obtain modified polybutylene terephthalate doped with antimony white.

[0228] The mass ratio of antimony white powder to aluminum chloride powder is 3:1.

[0229] The mass fraction of antimony white powder in the potassium hydroxide alkaline solution is 7%, and the alkaline solution is kept in excess.

[0230] The mass concentration of alumina composite material adsorbed on the surface of antimony white powder in n-pentane is 27g / L.

[0231] The 3-aminopropyltriethoxysilane is 4% by weight of the alumina composite material adsorbed on the surface of the antimony white powder.

[0232] The mass fraction of monobutyl maleate in the modified polybutylene terephthalate doped with antimony white is 1%.

[0233] The mass fraction of the initiator dicumyl peroxide in the modified polybutylene terephthalate doped with antimony white is 0.6%.

[0234] The mass fraction of the antimony white modified composite material in the antimony white-doped modified polybutylene terephthalate is 4%.

[0235] Monobutyl maleate, antimony white modified composite material and PBT are firstly coarsely ground and finely ground, and then extruded and granulated by an extruder to obtain modified polybutylene terephthalate powder doped with antimony white. In this process, the grafting rate is 1.7%.

[0236] High-speed stirring process: stirring speed is 2100 rpm, stirring time is 1 hour.

[0237] Ultrasonic dispersion process: dispersion time is 2.5 hours.

[0238] Calcination process: The calcination heating rate is 10°C / min, and the temperature is increased to 450°C.

[0239] Coarse grinding process: grinding speed is 650 rpm, and grinding time is 1 hour.

[0240] Fine grinding process: grinding speed is 2200rpm, grinding time is 2 hours.

[0241] Step 2: dissolving the modified polybutylene terephthalate doped with antimony white prepared in step 1 and polyethylene particles in a spinning solvent, controlling the pressure of the spinning solution to be 50-60 bar, to obtain a spinning solution;

[0242] The mass fraction of modified polybutylene terephthalate doped with antimony white and polyethylene particles in the spinning solution is 13.5%;

[0243] The mass fraction of the modified polybutylene terephthalate in the mixture of the modified polybutylene terephthalate doped with antimony white and the polyethylene particles is 2%.

[0244] The spinning solvent is 1,2-dichloroethylene, 2,3-dihydrodecafluoropentane, and 1,1,1,2-tetrafluoro-2-chloroethane, and the volume ratio of the three is 6:2:2.

[0245] Step 3: flash spinning the spinning solution prepared in step 2, and then pass the flash fiber through a web laying process, and then through a hot roller hot pressing molding and calendering process to obtain a polymer sheet; wherein the spinning temperature is 200-220°C and the spinning pressure is 50-60 bar. The performance test method is described above, and the test data results are shown in Table 1.

[0246] Comparative Example 7

[0247] A method for preparing a printable polymer sheet, comprising the following technical steps:

[0248] Step 1: (1) Dispersing antimony white powder and aluminum chloride powder in an alkaline potassium hydroxide solution, then stirring at high speed and ultrasonically dispersing, separating the precipitate, filtering and drying, and calcining to obtain an antimony white powder surface adsorbed aluminum oxide composite material; (2) Stirring at high speed and ultrasonically dispersing the antimony white powder surface adsorbed aluminum oxide composite material in an n-pentane solution, and then adding 3-aminopropyltriethoxysilane to react; after the reaction is completed, centrifugation is performed, and the solid is vacuum dried to prepare an antimony white modified composite material with adsorption functional groups; (3) Then, monobutyl maleate, initiator diisopropyl peroxide, antimony white modified composite material and PBT are coarsely ground and finely ground, and then melt-extruded and granulated by an extruder to obtain modified polybutylene terephthalate doped with antimony white.

[0249] The mass ratio of antimony white powder to aluminum chloride powder is 3:1.

[0250] The mass fraction of antimony white powder in the potassium hydroxide alkaline solution is 7%, and the alkaline solution is kept in excess.

[0251] The mass concentration of alumina composite material adsorbed on the surface of antimony white powder in n-pentane is 27g / L.

[0252] The 3-aminopropyltriethoxysilane is 4% by weight of the alumina composite material adsorbed on the surface of the antimony white powder.

[0253] The mass fraction of monobutyl maleate in the modified polybutylene terephthalate doped with antimony white is 1%.

[0254] The mass fraction of the initiator dicumyl peroxide in the modified polybutylene terephthalate doped with antimony white is 0.6%.

[0255] The mass fraction of the antimony white modified composite material in the antimony white-doped modified polybutylene terephthalate is 4%.

[0256] Monobutyl maleate, antimony white modified composite material and PBT are firstly coarsely ground and finely ground, and then extruded and granulated by an extruder to obtain modified polybutylene terephthalate powder doped with antimony white. In this process, the grafting rate is 1.7%.

[0257] High-speed stirring process: stirring speed is 2100 rpm, stirring time is 1 hour.

[0258] Ultrasonic dispersion process: dispersion time is 2.5 hours.

[0259] Calcination process: The calcination heating rate is 10°C / min, and the temperature is increased to 450°C.

[0260] Coarse grinding process: grinding speed is 650 rpm, and grinding time is 1 hour.

[0261] Fine grinding process: grinding speed is 2200rpm, grinding time is 2 hours.

[0262] Step 2: dissolving the modified polybutylene terephthalate doped with antimony white prepared in step 1 and polyethylene particles in a spinning solvent, controlling the pressure of the spinning solution to be 50-60 bar, to obtain a spinning solution;

[0263] The mass fraction of modified polybutylene terephthalate doped with antimony white and polyethylene particles in the spinning solution is 14.5%;

[0264] The mass fraction of the modified polybutylene terephthalate in the mixture of the modified polybutylene terephthalate doped with antimony white and the polyethylene particles is 2%.

[0265] The spinning solvent is 1,2-dichloroethylene, 2,3-dihydrodecafluoropentane, and 1,1,1,2-tetrafluoro-2-chloroethane, and the volume ratio of the three is 6:2:2.

[0266] Step 3: flash spinning the spinning solution prepared in step 2, and then pass the flash fiber through a web laying process, and then through a hot roller hot pressing molding and calendering process to obtain a polymer sheet; wherein the spinning temperature is 200-220°C and the spinning pressure is 50-60 bar. The performance test method is described above, and the test data results are shown in Table 1.

[0267] Comparative Example 8

[0268] A method for preparing a printable polymer sheet, comprising the following technical steps:

[0269] Step 1: (1) Dispersing antimony white powder and aluminum chloride powder in an alkaline potassium hydroxide solution, then stirring at high speed and ultrasonically dispersing, separating the precipitate, filtering and drying, and calcining to obtain an antimony white powder surface adsorbed aluminum oxide composite material; (2) Stirring at high speed and ultrasonically dispersing the antimony white powder surface adsorbed aluminum oxide composite material in an n-pentane solution, and then adding 3-aminopropyltriethoxysilane to react; after the reaction is completed, centrifugation is performed, and the solid is vacuum dried to prepare an antimony white modified composite material with adsorption functional groups; (3) Then, monobutyl maleate, initiator diisopropyl peroxide, antimony white modified composite material and PBT are coarsely ground and finely ground, and then melt-extruded and granulated by an extruder to obtain modified polybutylene terephthalate doped with antimony white.

[0270] The mass ratio of antimony white powder to aluminum chloride powder is 3:1.

[0271] The mass fraction of antimony white powder in the potassium hydroxide alkaline solution is 7%, and the alkaline solution is kept in excess.

[0272] The mass concentration of alumina composite material adsorbed on the surface of antimony white powder in n-pentane is 27g / L.

[0273] The 3-aminopropyltriethoxysilane is 4% by weight of the alumina composite material adsorbed on the surface of the antimony white powder.

[0274] The mass fraction of monobutyl maleate in the modified polybutylene terephthalate doped with antimony white is 1%.

[0275] The mass fraction of the initiator dicumyl peroxide in the modified polybutylene terephthalate doped with antimony white is 0.6%.

[0276] The mass fraction of the antimony white modified composite material in the antimony white-doped modified polybutylene terephthalate is 4%.

[0277] Monobutyl maleate, antimony white modified composite material and PBT are firstly coarsely ground and finely ground, and then extruded and granulated by an extruder to obtain modified polybutylene terephthalate powder doped with antimony white. In this process, the grafting rate is 1.7%.

[0278] High-speed stirring process: stirring speed is 2100 rpm, stirring time is 1 hour.

[0279] Ultrasonic dispersion process: dispersion time is 2.5 hours.

[0280] Calcination process: The calcination heating rate is 10°C / min, and the temperature is increased to 450°C.

[0281] Coarse grinding process: grinding speed is 650 rpm, and grinding time is 1 hour.

[0282] Fine grinding process: grinding speed is 2200rpm, grinding time is 2 hours.

[0283] Step 2: dissolving the modified polybutylene terephthalate doped with antimony white prepared in step 1 and polyethylene particles in a spinning solvent, controlling the pressure of the spinning solution to be 50-60 bar, to obtain a spinning solution;

[0284] The mass fraction of modified polybutylene terephthalate doped with antimony white and polyethylene particles in the spinning solution is 11.5%;

[0285] The mass fraction of the modified polybutylene terephthalate in the mixture of the modified polybutylene terephthalate doped with antimony white and the polyethylene particles is 0.5%.

[0286] The spinning solvent is 1,2-dichloroethylene, 2,3-dihydrodecafluoropentane, and 1,1,1,2-tetrafluoro-2-chloroethane, and the volume ratio of the three is 6:2:2.

[0287] Step 3: flash spinning the spinning solution prepared in step 2, and then pass the flash fiber through a web laying process, and then through a hot roller hot pressing molding and calendering process to obtain a polymer sheet; wherein the spinning temperature is 200-220°C and the spinning pressure is 50-60 bar. The performance test method is described above, and the test data results are shown in Table 1.

[0288] Comparative Example 9

[0289] A method for preparing a printable polymer sheet, comprising the following technical steps:

[0290] Step 1: (1) Dispersing antimony white powder and aluminum chloride powder in an alkaline potassium hydroxide solution, then stirring at high speed and ultrasonically dispersing, separating the precipitate, filtering and drying, and calcining to obtain an antimony white powder surface adsorbed aluminum oxide composite material; (2) Stirring at high speed and ultrasonically dispersing the antimony white powder surface adsorbed aluminum oxide composite material in an n-pentane solution, and then adding 3-aminopropyltriethoxysilane to react; after the reaction is completed, centrifugation is performed, and the solid is vacuum dried to prepare an antimony white modified composite material with adsorption functional groups; (3) Then, monobutyl maleate, initiator diisopropyl peroxide, antimony white modified composite material and PBT are coarsely ground and finely ground, and then melt-extruded and granulated by an extruder to obtain modified polybutylene terephthalate doped with antimony white.

[0291] The mass ratio of antimony white powder to aluminum chloride powder is 3:1.

[0292] The mass fraction of antimony white powder in the potassium hydroxide alkaline solution is 7%, and the alkaline solution is kept in excess.

[0293] The mass concentration of alumina composite material adsorbed on the surface of antimony white powder in n-pentane is 27g / L.

[0294] The 3-aminopropyltriethoxysilane is 4% by weight of the alumina composite material adsorbed on the surface of the antimony white powder.

[0295] The mass fraction of monobutyl maleate in the modified polybutylene terephthalate doped with antimony white is 1%.

[0296] The mass fraction of the initiator dicumyl peroxide in the modified polybutylene terephthalate doped with antimony white is 0.6%.

[0297] The mass fraction of the antimony white modified composite material in the antimony white-doped modified polybutylene terephthalate is 4%.

[0298] Monobutyl maleate, antimony white modified composite material and PBT are firstly coarsely ground and finely ground, and then extruded and granulated by an extruder to obtain modified polybutylene terephthalate powder doped with antimony white. In this process, the grafting rate is 1.7%.

[0299] High-speed stirring process: stirring speed is 2100 rpm, stirring time is 1 hour.

[0300] Ultrasonic dispersion process: dispersion time is 2.5 hours.

[0301] Calcination process: The calcination heating rate is 10°C / min, and the temperature is increased to 450°C.

[0302] Coarse grinding process: grinding speed is 650 rpm, and grinding time is 1 hour.

[0303] Fine grinding process: grinding speed is 2200rpm, grinding time is 2 hours.

[0304] Step 2: dissolving the modified polybutylene terephthalate doped with antimony white prepared in step 1 and polyethylene particles in a spinning solvent, controlling the pressure of the spinning solution to be 50-60 bar, to obtain a spinning solution;

[0305] The mass fraction of modified polybutylene terephthalate doped with antimony white and polyethylene particles in the spinning solution is 11.5%;

[0306] The mass fraction of the modified polybutylene terephthalate in the mixture of the modified polybutylene terephthalate doped with antimony white and the polyethylene particles is 1%.

[0307] The spinning solvent is 1,2-dichloroethylene, 2,3-dihydrodecafluoropentane, and 1,1,1,2-tetrafluoro-2-chloroethane, and the volume ratio of the three is 6:2:2.

[0308] Step 3: flash spinning the spinning solution prepared in step 2, and then pass the flash fiber through a web laying process, and then through a hot roller hot pressing molding and calendering process to obtain a polymer sheet; wherein the spinning temperature is 200-220°C and the spinning pressure is 50-60 bar. The performance test method is described above, and the test data results are shown in Table 1.

[0309] Comparative Example 10

[0310] A method for preparing a printable polymer sheet, comprising the following technical steps:

[0311] Step 1: (1) Dispersing antimony white powder and aluminum chloride powder in an alkaline potassium hydroxide solution, then stirring at high speed and ultrasonically dispersing, separating the precipitate, filtering and drying, and calcining to obtain an antimony white powder surface adsorbed aluminum oxide composite material; (2) Stirring at high speed and ultrasonically dispersing the antimony white powder surface adsorbed aluminum oxide composite material in an n-pentane solution, and then adding 3-aminopropyltriethoxysilane to react; after the reaction is completed, centrifugation is performed, and the solid is vacuum dried to prepare an antimony white modified composite material with adsorption functional groups; (3) Then, monobutyl maleate, initiator diisopropyl peroxide, antimony white modified composite material and PBT are coarsely ground and finely ground, and then melt-extruded and granulated by an extruder to obtain modified polybutylene terephthalate doped with antimony white.

[0312] The mass ratio of antimony white powder to aluminum chloride powder is 3:1.

[0313] The mass fraction of antimony white powder in the potassium hydroxide alkaline solution is 7%, and the alkaline solution is kept in excess.

[0314] The mass concentration of alumina composite material adsorbed on the surface of antimony white powder in n-pentane is 27g / L.

[0315] The 3-aminopropyltriethoxysilane is 4% by weight of the alumina composite material adsorbed on the surface of the antimony white powder.

[0316] The mass fraction of monobutyl maleate in the modified polybutylene terephthalate doped with antimony white is 1%.

[0317] The mass fraction of the initiator dicumyl peroxide in the modified polybutylene terephthalate doped with antimony white is 0.6%.

[0318] The mass fraction of the antimony white modified composite material in the antimony white-doped modified polybutylene terephthalate is 4%.

[0319] Monobutyl maleate, antimony white modified composite material and PBT are firstly coarsely ground and finely ground, and then extruded and granulated by an extruder to obtain modified polybutylene terephthalate powder doped with antimony white. In this process, the grafting rate is 1.7%.

[0320] High-speed stirring process: stirring speed is 2100 rpm, stirring time is 1 hour.

[0321] Ultrasonic dispersion process: dispersion time is 2.5 hours.

[0322] Calcination process: The calcination heating rate is 10°C / min, and the temperature is increased to 450°C.

[0323] Coarse grinding process: grinding speed is 650 rpm, and grinding time is 1 hour.

[0324] Fine grinding process: grinding speed is 2200rpm, grinding time is 2 hours.

[0325] Step 2: dissolving the modified polybutylene terephthalate doped with antimony white prepared in step 1 and polyethylene particles in a spinning solvent, controlling the pressure of the spinning solution to be 50-60 bar, to obtain a spinning solution;

[0326] The mass fraction of modified polybutylene terephthalate doped with antimony white and polyethylene particles in the spinning solution is 11.5%;

[0327] The mass fraction of the modified polybutylene terephthalate in the mixture of the modified polybutylene terephthalate doped with antimony white and the polyethylene particles is 3.5%.

[0328] The spinning solvent is 1,2-dichloroethylene, 2,3-dihydrodecafluoropentane, and 1,1,1,2-tetrafluoro-2-chloroethane, and the volume ratio of the three is 6:2:2.

[0329] Step 3: flash spinning the spinning solution prepared in step 2, and then pass the flash fiber through a web laying process, and then through a hot roller hot pressing molding and calendering process to obtain a polymer sheet; wherein the spinning temperature is 200-220°C and the spinning pressure is 50-60 bar. The performance test method is described above, and the test data results are shown in Table 1.

[0330] Comparative Example 11

[0331] A method for preparing a printable polymer sheet, comprising the following technical steps:

[0332] Step 1: (1) Dispersing antimony white powder and aluminum chloride powder in an alkaline potassium hydroxide solution, then stirring at high speed and ultrasonically dispersing, separating the precipitate, filtering and drying, and calcining to obtain an antimony white powder surface adsorbed aluminum oxide composite material; (2) Stirring at high speed and ultrasonically dispersing the antimony white powder surface adsorbed aluminum oxide composite material in an n-pentane solution, and then adding 3-aminopropyltriethoxysilane to react; after the reaction is completed, centrifugation is performed, and the solid is vacuum dried to prepare an antimony white modified composite material with adsorption functional groups; (3) Then, monobutyl maleate, initiator diisopropyl peroxide, antimony white modified composite material and PBT are coarsely ground and finely ground, and then melt-extruded and granulated by an extruder to obtain modified polybutylene terephthalate doped with antimony white.

[0333] The mass ratio of antimony white powder to aluminum chloride powder is 3:1.

[0334] The mass fraction of antimony white powder in the potassium hydroxide alkaline solution is 7%, and the alkaline solution is kept in excess.

[0335] The mass concentration of alumina composite material adsorbed on the surface of antimony white powder in n-pentane is 27g / L.

[0336] The 3-aminopropyltriethoxysilane is 4% by weight of the alumina composite material adsorbed on the surface of the antimony white powder.

[0337] The mass fraction of monobutyl maleate in the modified polybutylene terephthalate doped with antimony white is 1%.

[0338] The mass fraction of the initiator dicumyl peroxide in the modified polybutylene terephthalate doped with antimony white is 0.6%.

[0339] The mass fraction of the antimony white modified composite material in the antimony white-doped modified polybutylene terephthalate is 4%.

[0340] Monobutyl maleate, antimony white modified composite material and PBT are firstly coarsely ground and finely ground, and then extruded and granulated by an extruder to obtain modified polybutylene terephthalate powder doped with antimony white. In this process, the grafting rate is 1.7%.

[0341] High-speed stirring process: stirring speed is 2100 rpm, stirring time is 1 hour.

[0342] Ultrasonic dispersion process: dispersion time is 2.5 hours.

[0343] Calcination process: The calcination heating rate is 10°C / min, and the temperature is increased to 450°C.

[0344] Coarse grinding process: grinding speed is 650 rpm, and grinding time is 1 hour.

[0345] Fine grinding process: grinding speed is 2200rpm, grinding time is 2 hours.

[0346] Step 2: dissolving the modified polybutylene terephthalate doped with antimony white prepared in step 1 and polyethylene particles in a spinning solvent, controlling the pressure of the spinning solution to be 50-60 bar, to obtain a spinning solution;

[0347] The mass fraction of modified polybutylene terephthalate doped with antimony white and polyethylene particles in the spinning solution is 11.5%;

[0348] The mass fraction of the modified polybutylene terephthalate in the mixture of the modified polybutylene terephthalate doped with antimony white and the polyethylene particles is 4%.

[0349] The spinning solvent is 1,2-dichloroethylene, 2,3-dihydrodecafluoropentane, and 1,1,1,2-tetrafluoro-2-chloroethane, and the volume ratio of the three is 6:2:2.

[0350] Step 3: flash spinning the spinning solution prepared in step 2, and then pass the flash fiber through a web laying process, and then through a hot roller hot pressing molding and calendering process to obtain a polymer sheet; wherein the spinning temperature is 200-220°C and the spinning pressure is 50-60 bar. The performance test method is described above, and the test data results are shown in Table 1.

[0351] Table 1

[0352]

[0353] The above is only a preferred embodiment of the present invention. It should be pointed out that ordinary technicians in this technical field can make several improvements and modifications without departing from the concept of the present invention. These improvements and modifications should also be regarded as within the scope of protection of the present invention.

Claims

1. A printable polymer sheet, characterized in that: Its raw material is mainly polyethylene, with a gram weight of 46 to 76 g / m 2 ; The positive printing surface strength is greater than 3.4 m / s; The reverse printing surface strength is greater than 2.8 m / s; Smoothness is 25 to 50 seconds; Burst resistance index is 6~12kPa·m 2 / g; The method for preparing the printable polymer sheet comprises the following technical steps: Step 1: (1) dispersing antimony white powder and aluminum chloride powder in an alkaline potassium hydroxide solution, and then stirring at high speed and ultrasonically dispersing, separating the precipitate, filtering and drying, and calcining to obtain an antimony white powder surface adsorbed aluminum oxide composite material; (2) stirring at high speed and ultrasonically dispersing the antimony white powder surface adsorbed aluminum oxide composite material in an n-pentane solution, and then adding 3-aminopropyltriethoxysilane to react; after the reaction is completed, centrifugation is performed, and the solid is vacuum dried to prepare an antimony white modified composite material with adsorption functional groups; (3) Then, monobutyl maleate, initiator diisopropylbenzene peroxide, antimony white modified composite material and PBT are coarsely ground and finely ground, and then melt-extruded and granulated by an extruder to obtain modified polybutylene terephthalate doped with antimony white; The mass ratio of antimony white powder to aluminum chloride powder is 2:1 to 4:1; The mass fraction of antimony white powder in potassium hydroxide alkaline solution is 5-10%; The mass concentration of the alumina composite material adsorbed on the surface of antimony white powder in n-pentane is 15-50 g / L; The mass fraction of the antimony white modified composite material in the modified polybutylene terephthalate doped with antimony white is 2 to 5%. Step 2: dissolving the modified polybutylene terephthalate doped with antimony white prepared in step 1 and polyethylene particles in a spinning solvent, controlling the pressure of the spinning solution to be 40 to 80 bar, to obtain a spinning solution; The mass fraction of modified polybutylene terephthalate doped with antimony white and polyethylene particles in the spinning solution is 10-13%; The mass fraction of the modified polybutylene terephthalate in the mixture of the modified polybutylene terephthalate doped with antimony white and the polyethylene particles is 1.5 to 3%. Step three: flash-spin the spinning solution prepared in step two, and then pass the flash-spun fiber through a web laying procedure, and then through a hot roller heat pressing and calendering process to obtain a polymer sheet; wherein the spinning temperature is 200-220°C, and the spinning pressure is 40-80 bar.

2. A printable polymer sheet according to claim 1, characterized in that: The positive printing surface strength of the polymer sheet is 4.4 to 5.4 m / s or 5.4 to 6.4 m / s.

3. A printable polymer sheet according to claim 1, characterized in that: The reverse printing surface strength of the polymer sheet is 3.8 to 4.8 m / s or 4.8 to 5.8 m / s.

4. A printable polymer sheet according to claim 1, characterized in that: The smoothness of the polymer sheet is 35 to 42 seconds or 42 to 50 seconds.

5. The printable polymer sheet according to claim 1, characterized in that: The bursting index of polymer sheet is 6~8kPa·m 2 / g or 8~10kPa·m 2 / g or 10~12kPa·m 2 / g.

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