A modified opening agent, a method for preparing the same, and a printable modified biodegradable material and a method for preparing the same

Abstract

The application discloses a modified opening agent, a preparation method thereof, and a modified biodegradable material easy to print and a preparation method thereof. The preparation raw materials of the modified opening agent comprise an opening agent containing a carbon-carbon double bond, a grafting monomer containing a mercapto group and two or more hydroxyl groups or carboxyl groups, a photoinitiator, and a solvent. The modified biodegradable material is used, the grafting monomer is reacted with the opening agent, the opening agent can be migrated to the surface of the material, the hydrophilic functional groups are brought, the adhesion of water and ink is improved, the printing is easy, and no color is dropped. The modified biodegradable material can be widely applied to shopping bags, vest bags and the like.

Description

TECHNICAL FIELD

[0001] The present application relates to a modified biodegradable material, in particular to a modified opening agent and a preparation method thereof, and an easy-to-print modified biodegradable material and a preparation method thereof. BACKGROUND

[0002] Biodegradable plastics refer to a class of plastics that are degraded by microorganisms such as bacteria, molds (fungi) and algae existing in nature. The ideal biodegradable plastic is a polymer material that has excellent performance, can be completely decomposed by environmental microorganisms after being discarded, and is ultimately inorganicized to become a part of the carbon cycle in nature.

[0003] PBAT belongs to thermoplastic biodegradable plastics, and is a copolymer of butylene adipate and butylene terephthalate, which has the properties of PBA and PBT, and has good ductility and elongation at break, and also has good heat resistance and impact performance. It is the most commonly used biodegradable material for film bags. Polylactic acid (PLA) is a polyester polymer obtained by polymerization of lactic acid, and is a completely biodegradable material. As a film bag material, the material needs to be modified, but the addition of opening agents, lubricants and the like will cause the adhesion of printing ink to decrease, affecting the printing effect of the product. The ink is mainly water and part of alcohol solvent, and the resin of the water-soluble system is used as the connecting material. Most of the inks still use traditional organic solvents, which are not environmentally friendly and harmful to the body. At present, the use of water-based ink printing has become the development trend of the printing industry, but there is no report to solve the problem of poor water-based ink printing effect.

[0004] Patent CN 115521589 A fills diatomite to prepare a biodegradable film, which is not easy to fade after printing with oily ink, and the pattern has bright color and high clarity, but the problem of poor water-based ink adhesion is not solved.

[0005] Patent CN 113736226 A modifies metal-organic frameworks with a coupling agent to make them have the function of adsorbing small molecules to remove odor, and can also be uniformly dispersed in PBAT together with fillers to prepare a PBAT composite film, but the problem of poor water-based ink adhesion is not solved.

[0006] Patent CN 113652063 A uses PBAT, PLA, nano calcium carbonate, surface modifier, chain extender, lubricant, opening agent and antioxidant as raw materials to prepare a film, but the problem of poor water-based ink adhesion is not solved.

[0007] It can be seen that the modified biodegradable film bag materials prepared by the prior art have not solved the problem of poor water-based ink adhesion, and new solutions need to be found to solve the above problems so that water-based ink can be successfully printed. SUMMARY

[0008] To solve the above technical problems, the present application first provides a modified opening agent and a preparation method thereof, wherein a grafting monomer containing a mercapto group and a plurality of hydroxyl groups or carboxyl groups is used to modify the opening agent.

[0009] Meanwhile, the present application also provides an easily-printable modified biodegradable material and a preparation method thereof, wherein the above-mentioned modified opening agent is used. After the opening agent migrates to the surface of the material, the hydrophilic functional groups can improve the adhesion of water-based ink, so that the material can be easily printed without color loss. In addition, because the opening agent can easily migrate to the surface and the selected grafting monomer has a large number of hydrophilic functional groups, the amount of grafting monomer required to be added is small, which can greatly improve the adhesion effect of water-based ink on the surface of the film, and effectively solve the problem of poor adhesion of water-based ink on the surface of the printed biodegradable material.

[0010] To achieve the above-mentioned purposes, the technical solutions adopted by the present application are as follows:

[0011] In one aspect, the present application provides a modified opening agent, and the preparation raw materials thereof include:

[0012] an opening agent containing a carbon-carbon double bond,

[0013] a grafting monomer containing a mercapto group and two or more hydroxyl groups or carboxyl groups, the amount of which is 50-100% of the molar amount of the carbon-carbon double bond contained in the opening agent, preferably 60-90%;

[0014] a photoinitiator, the amount of which is 1-15% of the molar amount of the grafting monomer, preferably 2-4%;

[0015] a solvent, the amount of which is 5-10 times, preferably 6-9 times, of the total mass of the opening agent containing a carbon-carbon double bond, the grafting monomer containing a mercapto group and two or more hydroxyl groups or carboxyl groups, and the light stabilizer.

[0016] Further, the opening agent containing a carbon-carbon double bond is selected from one or more of unsaturated fatty amides containing a carbon-carbon double bond, preferably one or more of erucic acid amide, oleic acid amide.

[0017] Further, the grafting monomer containing a mercapto group and two or more hydroxyl groups or carboxyl groups is selected from one or more of mercapto compounds containing 2-4 hydroxyl groups or carboxyl groups, preferably one or more of thiomalic acid, (2S)-2-hydroxy-3-mercaptopropionic acid, 2-thiouracil-5-carboxylic acid, cis-1-(3-mercapto-1-oxopropyl)-2,5-piperidinedicarboxylic acid.

[0018] Further, the photoinitiator is selected from one or more of ketone photoinitiators, preferably one or more of 2,2-dimethoxy-2-phenylphenylethanone (DMPA), benzophenone.

[0019] Further, the solvent is a solvent capable of dissolving the grafting monomer, the photoinitiator, and the opening agent, such as amide DMAC (dimethylacetamide), DMP (dimethylpropionamide), DEF (diethylformamide), DMF (N,N-dimethylformamide), etc., and preferably N,N-dimethylformamide (DMF).

[0020] The application also provides a preparation method of the modified opening agent, comprising the following steps:

[0021] (1) mixing the opening agent containing a carbon-carbon double bond, the grafting monomer containing a mercapto group and two or more hydroxyl groups or carboxyl groups, the photoinitiator, and a solvent, and stirring until completely dissolved to obtain a solution;

[0022] (2) placing the solution of step (1) in an ultraviolet light irradiation condition in a nitrogen environment, stirring to perform a reaction, and then washing and drying to obtain the modified opening agent.

[0023] Further, in step (1), the stirring temperature is 10-40°C, preferably 20-35°C, and the stirring speed is 50-200 rpm, preferably 60-150 rpm.

[0024] Further, in step (2), the ultraviolet light irradiation has a power of 36-72 W, and a wavelength of 200-360 nm, preferably 250-350 nm.

[0025] Further, in step (2), the reaction has a time of 10-30 min, preferably 15-25 min, and a temperature of 10-40°C, preferably 20-35°C.

[0026] The stirring speed is 50-200 rpm, preferably 60-150 rpm.

[0027] Further, in step (2), the washing and drying are conventional operations in the art and do not have special requirements, and in some specific examples of the application, the method is preferably as follows: after the reaction is completed, the reaction solution is vacuum rotary evaporated once to dry, then washed with anhydrous ethanol, vacuum rotary evaporated twice to dry, and dried to obtain the product.

[0028] Preferably, the vacuum rotary evaporation once has a vacuum degree of -0.03 to -0.1 MPa, preferably -0.05 to -0.08 MPa, a temperature of 50-120°C, preferably 70-100°C, and a time of 3-8 h, preferably 4-6 h.

[0029] The vacuum rotary evaporation twice has a vacuum degree of -0.03 to -0.1 MPa, preferably -0.05 to -0.08 MPa, a temperature of 40-60°C, preferably 45-55°C, and a time of 1-4 h, preferably 2-3 h.

[0030] The amount of the anhydrous ethanol is 3-10 times, preferably 5-8 times of the mass of the remaining solid after vacuum rotary evaporation drying;

[0031] The drying temperature is 50-80 DEG C, preferably 60-75 DEG C, and the drying time is 2-5 h, preferably 3-4 h.

[0032] The modified opening agent prepared by the above method can be used in the field of modified biodegradable materials, and can solve the problem of poor water ink adhesion of printed biodegradable materials.

[0033] In another aspect, the application also provides an easy-to-print modified biodegradable material, which contains the above-mentioned modified opening agent, and is specifically prepared from raw materials including the following weight percentages:

[0034] PBAT, 60-93%, preferably 70-86%;

[0035] PLA, 1-10%, preferably 3-6%;

[0036] Modified opening agent, 0.2-1%, preferably 0.3-0.6%;

[0037] Filler, 5-30%, preferably 10-25%.

[0038] Further, the PBAT (polybutylene adipate-co-terephthalate) has a melt index of 1-5 g / 10 min at 190 DEG C under a load of 2.16 kg.

[0039] Further, the PLA (polylactic acid) has a melt index of 3-30 g / 10 min, preferably 5-25 g / 10 min, at 190 DEG C under a load of 2.16 kg.

[0040] Further, the filler is selected from one or more of talc, calcium carbonate and other mineral powders.

[0041] The application also provides a preparation method of the easy-to-print modified biodegradable material as described above, comprising the following steps:

[0042] 1) mixing PBAT, PLA, modified opening agent and filler in a high-speed mixer;

[0043] 2) extruding and granulating the mixture obtained in step 1) through a twin-screw extruder to obtain the easy-to-print modified biodegradable material.

[0044] Further, in step 1), the mixing conditions of the high-speed mixer are as follows: temperature 10-40 DEG C, rotation speed 50-400 rpm, preferably 100-300 rpm, and mixing time 3-8 min, preferably 4-7 min.

[0045] Further, in step 2), the operating conditions of the twin-screw extruder are as follows: screw temperature is 150-190℃, preferably 160-180℃, and rotation speed is 150-500rpm, preferably 200-400rpm.

[0046] Compared with the prior art, the technical scheme of the present application has the beneficial effects that:

[0047] The grafting monomer containing sulfydryl and polyhydroxy or carboxyl is used to prepare a modified opening agent, which is used in printing of biodegradable materials to effectively solve the problem of poor water ink adhesion. The prepared easily-printed modified biodegradable material uses the grafting monomer to react with the opening agent, so that the opening agent migrates to the material surface and improves the water ink adhesion due to the hydrophilic functional groups, thereby being easily printed, not fading, and due to the fact that the opening agent is easy to migrate to the surface and the selected grafting monomer has more hydrophilic functional groups, a small amount of grafting monomer can greatly improve the adhesion effect of water ink on the film surface.

[0048] The modified biodegradable material can be widely applied to the field of film bags, for example, in preparation of shopping bags, vest bags and the like. BRIEF DESCRIPTION OF DRAWINGS

[0049] Figure 1 The adhesion effect of the biodegradable material prepared for Comparative Example 1 after water ink printing. DETAILED DESCRIPTION

[0050] The present application will be further described below through specific examples, and the examples described in the present application are only used to illustrate the present application and do not limit the scope of the present application.

[0051] The main raw material information used in the examples and comparative examples is shown in Table 1, and other materials are ordinary commercially available materials unless otherwise specified.

[0052] Table 1 Main raw material information

[0053]

[0054]

[0055] The main test methods used in the examples and comparative examples of the present application are as follows:

[0056] Water ink adhesion test: the water ink adhesion fastness is tested according to the test method for liquid ink adhesion fastness in GB / T 13217.7-2009.

[0057] Opening performance: the friction coefficient of the film is tested according to the test method for friction coefficient of plastic film and sheet in GB / T 10006-88.

[0058] The main equipment used in the examples and comparative examples of the present application is as follows:

[0059] High-speed mixer: 120L pot-type high-speed mixer, Suzhou Songyuan Environmental Protection Technology Co., Ltd.

[0060] Twin-screw extruder: The twin-screw extruder used is a product of Kobe Long Machinery Co., Ltd., model ZSK32Mc.

[0061] Example 1

[0062] The raw materials for preparing the modified opening agent include:

[0063] Opening agent: erucic acid amide;

[0064] Grafting monomer: thiomalic acid, the molar amount of sulfhydryl contained is 80% of the molar amount of carbon-carbon double bonds in erucic acid amide;

[0065] Photoinitiator: 2,2-dimethoxy-2-phenylacetophenone (DMPA), 3% of the molar amount of the grafting monomer;

[0066] Solvent: DMF, the amount used is 7 times the total mass of the opening agent, grafting monomer and photoinitiator.

[0067] According to the above proportions, erucic acid amide, thiomalic acid, DMPA and DMF are weighed and added to the reactor, stirred at room temperature, the stirring temperature is 30°C, the stirring speed is 100 rpm, and the solution is obtained after stirring until complete dissolution;

[0068] Nitrogen is introduced to replace the air in the reactor, the replacement time is 4 min, after the replacement is completed, it is irradiated with a UV lamp, the power is 72w, the wavelength of the UV light is 300nm, it is stirred at a speed of 100 rpm at 30°C for 20 min, after the reaction is completed, it is vacuumed, the vacuum degree is -0.06MPa, it is rotary evaporated and dried at 80°C for 5h, the dried sample is washed with 7 times its mass of anhydrous ethanol, vacuumed again, the vacuum degree is -0.06MPa, rotary evaporated and dried at 50°C for 2.5h, then baked at 70°C for 3.5h, and the modified opening agent is obtained.

[0069] Preparation of easy-to-print modified biodegradable material, the total mass of 100kg of raw materials is prepared according to the following weight percentage:

[0070] PBAT TH801T, 75.5%;

[0071] PLA LX575, 4%;

[0072] Modified opening agent, 0.5%;

[0073] Filler talc, 20%.

[0074] The weighed PBAT, PLA, modified opening agent, and filler are uniformly mixed in a high-speed mixer, the operating temperature of the high-speed mixer is 30°C, the rotating speed is 200 rpm, and the mixing time is 6 min, to obtain a premix;

[0075] The premix is extruded by a twin-screw extruder, and granulated, wherein the screw temperature is segmented from the feeding port to the die head as 160°C, 180°C, 180°C, 180°C, 180°C, 180°C, 175°C, 175°C, 175°C, 170°C, 190°C, and the rotating speed is 300 rpm, to obtain the easy-to-print modified biodegradable material.

[0076] Example 2

[0077] The modified opening agent is prepared, and the raw materials include:

[0078] The opening agent is oleic acid amide;

[0079] The grafting monomer is (2S)-2-hydroxy-3-mercapto propionic acid, and the molar amount of the contained mercapto group is 50% of the molar amount of the carbon-carbon double bond in the oleic acid amide;

[0080] The photoinitiator is benzophenone, and the molar amount is 1% of the molar amount of the grafting monomer;

[0081] The solvent is DMF, and the amount is 5 times the total mass of the opening agent, the grafting monomer, and the photoinitiator.

[0082] The oleic acid amide, the (2S)-2-hydroxy-3-mercapto propionic acid, the benzophenone, and the DMF are weighed according to the above proportions and added to a reactor, stirred at room temperature, the stirring temperature is 10°C, the rotating speed is 50 rpm, and the solution is obtained after stirring until completely dissolved;

[0083] Nitrogen is introduced to replace the air in the reactor, the replacement time is 3 min, after the replacement is completed, the solution is irradiated by a UV lamp with a power of 60 w and a wavelength of 200 nm, stirred at a rotating speed of 50 rpm at 10°C for 10 min, after the reaction is completed, vacuum is applied, the vacuum degree is -0.03 MPa, and the dried sample is dried by rotary evaporation at 50°C for 3 h, washed with 3 times the mass of anhydrous ethanol, vacuumed again with a vacuum degree of -0.03 MPa, dried by rotary evaporation at 40°C for 1 h, and then dried at 50°C for 2 h, to obtain the modified opening agent.

[0084] The easy-to-print modified biodegradable material is prepared, and the raw materials with a total mass of 100 kg are prepared according to the following weight percentages:

[0085] PBAT T16, 93%;

[0086] PLA L130, 1%;

[0087] Modified opening agent, 1%;

[0088] Filler calcium carbonate, 5%.

[0089] The weighed PBAT, PLA, modified opening agent, and filler were mixed uniformly in a high-speed mixer, the operating temperature of the high-speed mixer was 30°C, the rotating speed was 300 rpm, and the mixing time was 7 min, to obtain a premix;

[0090] The premix was extruded through a twin-screw extruder, and granulated, wherein the screw temperature was segmented from the feeding port to the die head as 150°C, 190°C, 190°C, 180°C, 180°C, 180°C, 175°C, 175°C, 175°C, 170°C, 190°C, and the rotating speed was 150 rpm, to obtain the easy-to-print modified biodegradable material.

[0091] Example 3

[0092] The modified opening agent was prepared, and the raw materials included:

[0093] Opening agent: erucic acid amide;

[0094] Grafting monomer: 2-thiouracil-5-carboxylic acid, the molar amount of the contained mercapto group was 70% of the molar amount of the carbon-carbon double bond in erucic acid amide;

[0095] Photoinitiator: 2,2-dimethoxy-2-phenylacetophenone (DMPA), the molar amount was 2% of the molar amount of the grafting monomer;

[0096] Solvent: DMF, the amount was 6 times the total mass of the opening agent, the grafting monomer, and the photoinitiator.

[0097] The erucic acid amide, 2-thiouracil-5-carboxylic acid, DMPA, and DMF were weighed according to the above proportions and added to a reactor, stirred at room temperature, the stirring temperature was 20°C, the rotating speed was 60 rpm, and the solution was obtained after stirring until completely dissolved;

[0098] Nitrogen was introduced to replace the air in the reactor, the replacement time was 5 min, after the replacement was completed, the solution was irradiated with a UV lamp, the power was 40 w, the wavelength of the UV light was 250 nm, the stirring was performed at a rotating speed of 60 rpm at 20°C for 15 min, after the reaction was completed, vacuum was applied, the vacuum degree was -0.05 MPa, and the dried sample was dried by rotary evaporation at 70°C for 4 h, the dried sample was washed with 5 times the mass of anhydrous ethanol, vacuum was applied again, the vacuum degree was -0.05 MPa, and the sample was dried by rotary evaporation at 45°C for 2 h, and then dried at 60°C for 3 h, to obtain the modified opening agent.

[0099] The easy-to-print modified biodegradable material was prepared, and the raw materials with a total mass of 100 kg were prepared according to the following weight percentages:

[0100] PBAT C1200, 86.4%;

[0101] PLA FY401, 3%;

[0102] Modified opening agent, 0.6%;

[0103] Filler talc, 10%.

[0104] The weighed PBAT, PLA, modified opening agent, and filler were mixed uniformly in a high-speed mixer, the operating temperature of the high-speed mixer was 20℃, the rotating speed was 100rpm, and the mixing time was 4min, to obtain a premix;

[0105] The premix was extruded by a twin-screw extruder, and granulated, wherein the screw temperature was segmented from the feeding port to the die head as 160℃, 180℃, 190℃, 190℃, 190℃, 190℃, 175℃, 175℃, 175℃, 170℃, 180℃, and the rotating speed was 200rpm, to obtain the easy-to-print modified biodegradable material.

[0106] Example 4

[0107] The modified opening agent was prepared, and the raw materials included:

[0108] Opening agent: erucic acid amide;

[0109] Grafting monomer: cis-1-(3-mercapto-1-oxopropyl)-2,5-piperidine dicarboxylic acid, the molar amount of the contained mercapto group was 90% of the molar amount of the carbon-carbon double bond in erucic acid amide;

[0110] Photoinitiator: benzophenone, the molar amount was 4% of the molar amount of the grafting monomer;

[0111] Solvent: DMF, the amount was 8 times of the total mass of the opening agent, the grafting monomer, and the photoinitiator.

[0112] The erucic acid amide, cis-1-(3-mercapto-1-oxopropyl)-2,5-piperidine dicarboxylic acid, benzophenone, and DMF were weighed according to the above proportions and added to a reactor, and stirred at room temperature, the stirring temperature was 35℃, the rotating speed was 150rpm, and the solution was obtained after stirring until complete dissolution;

[0113] The air in the reactor was replaced with nitrogen for 5 min, and then irradiated with a UV lamp at a power of 36 W and a wavelength of 350 nm at 35°C for 25 min under stirring at a speed of 150 rpm. After the reaction was completed, the sample was dried by rotary evaporation at 100°C for 6 h under a vacuum of -0.08 MPa. The dried sample was washed with 8 times its mass of anhydrous ethanol, and then dried by rotary evaporation at 55°C for 3 h under a vacuum of -0.08 MPa, and then at 75°C for 4 h.

[0114] The raw materials for preparing the easily printable modified biodegradable material were prepared according to the following weight percentages, with a total mass of 100 kg:

[0115] PBAT Ecoworld 1908, 68.7%;

[0116] PLA L105, 6%;

[0117] Modified opening agent, 0.3%;

[0118] Filler calcium carbonate, 25%.

[0119] The weighed PBAT, PLA, modified opening agent, and filler were uniformly mixed in a high-speed mixer, the operating temperature of the high-speed mixer was 10°C, the speed was 50 rpm, and the mixing time was 3 min, to obtain a premix;

[0120] The premix was extruded through a twin-screw extruder and then granulated, wherein the screw temperature was set in sections from the feeding port to the die head as 170°C, 170°C, 190°C, 190°C, 190°C, 180°C, 180°C, 175°C, 175°C, 170°C, 175°C, and the speed was 400 rpm, to obtain the easily printable modified biodegradable material.

[0121] Example 5

[0122] The raw materials for preparing the modified opening agent included:

[0123] Opening agent: oleic acid amide;

[0124] Grafting monomer: cis-1-(3-mercapto-1-oxopropyl)-2,5-piperidinedicarboxylic acid, the molar amount of the contained mercapto group was 100% of the molar amount of the carbon-carbon double bond in the oleic acid amide;

[0125] Photoinitiator: 2,2-dimethoxy-2-phenylacetophenone (DMPA), the molar amount was 5% of the molar amount of the grafting monomer;

[0126] Solvent: DMF, the amount was 10 times the total mass of the opening agent, grafting monomer, and photoinitiator.

[0127] The erucamide, cis-1-(3-mercapto-1-oxopropyl)-2,5-piperidinedicarboxylic acid, DMPA, and DMF are weighed according to the above proportions and added to the reactor, stirred at room temperature, the stirring temperature is 40°C, the stirring speed is 200 rpm, and the solution is obtained by stirring until complete dissolution;

[0128] The air in the reactor is replaced with nitrogen for 4 min, then irradiated with a UV lamp, the power is 60 w, the wavelength of the UV light is 360 nm, the stirring speed is 200 rpm, and the reaction is carried out at 40°C for 30 min. After the reaction is completed, the vacuum degree is -0.1 MPa, the sample is dried by rotary evaporation at 120°C for 8 h, the dried sample is washed with 10 times the mass of anhydrous ethanol, the vacuum degree is -0.1 MPa, the sample is dried by rotary evaporation at 60°C for 4 h, and then dried at 80°C for 5 h to obtain the modified opening agent.

[0129] The easily printable modified biodegradable material is prepared by preparing raw materials with a total mass of 100 kg according to the following weight percentages:

[0130] PBAT T16, 60.8%;

[0131] PLA REVODE110, 9%;

[0132] Modified opening agent, 0.2%;

[0133] Filler talc, 30%.

[0134] The weighed PBAT, PLA, modified opening agent, and filler are uniformly mixed in a high-speed mixer, the operating temperature of the high-speed mixer is 40°C, the stirring speed is 400 rpm, and the mixing time is 8 min to obtain a premix;

[0135] The premix is extruded through a twin-screw extruder and granulated, wherein the screw temperature is segmented from the feeding port to the die head at 160°C, 180°C, 180°C, 180°C, 180°C, 180°C, 175°C, 175°C, 175°C, 170°C, 180°C, and the rotating speed is 500 rpm to obtain the easily printable modified biodegradable material.

[0136] Comparative Example 1

[0137] Referring to the method of Example 1, the only difference is that no grafting monomer thiomalic acid is added in the preparation process of the modified opening agent, and other operations and conditions remain unchanged to prepare the modified biodegradable material.

[0138] Comparative Example 2

[0139] Referring to the method of Example 1, the only difference is that the mixture of grafting monomer thiomalic acid and photoinitiator DMPA of the modified opening agent raw material is directly replaced with the modified opening agent, and other operations and conditions are unchanged, to prepare the modified biodegradable material.

[0140] Comparative Example 3

[0141] Referring to the method of Example 1, the only difference is that the combination of the opening agent and the modified raw material grafting monomer thiomalic acid and photoinitiator DMPA is used to replace the modified opening agent without pre-modification of the opening agent, and other operations and conditions are unchanged, to prepare the modified biodegradable material.

[0142] Comparative Example 4

[0143] Referring to the method of Example 1, the only difference is that the grafting monomer thiomalic acid is replaced with ethylene glycol in the preparation of the modified opening agent, and other operations and conditions are unchanged, to prepare the modified biodegradable material.

[0144] Comparative Example 5

[0145] Referring to the method of Example 1, the only difference is that the grafting monomer thiomalic acid is replaced with 3-(2-carboxyphenyl)propionic acid in the preparation of the modified opening agent, and other operations and conditions are unchanged, to prepare the modified biodegradable material.

[0146] Comparative Example 6

[0147] Referring to the method of Example 1, the only difference is that the grafting monomer thiomalic acid is replaced with 2-mercaptopyrrolidine in the preparation of the modified opening agent, and other operations and conditions are unchanged, to prepare the modified biodegradable material.

[0148] The modified biodegradable materials prepared in Examples 1-5 and Comparative Examples 1-3 are respectively subjected to water ink printing experiments, and the test results are shown in Table 2 below:

[0149] Table 2 Product performance test results

[0150]

[0151]

[0152] From the test results of each performance in Table 2, it can be seen that the easy-to-print modified biodegradable material prepared by the present application has the characteristics of high water ink adhesion and easy printing.

[0153] The above merely describes the preferred embodiments of the present application, and it should be noted that, for those skilled in the art, several improvements and supplements can be made without departing from the method of the present application, and these improvements and supplements should also be considered as the protection scope of the present application.

Claims

1. A modified opening agent characterized in that, The raw materials for preparation include: an opening agent containing carbon-carbon double bond, the opening agent containing carbon-carbon double bond is selected from one or more of unsaturated fatty amides containing carbon-carbon double bond; a grafting monomer, the grafting monomer is selected from a monomer containing mercapto and two or more hydroxyl or carboxyl, (2S)-2-hydroxy-3-mercaptopropionic acid or 2-thiouracil-5-carboxylic acid, the amount of which is 50-100% of the molar amount of carbon-carbon double bond contained in the opening agent in terms of the molar amount of mercapto contained; a photoinitiator, the amount of which is 1-15% of the molar amount of the grafting monomer; a solvent, the amount of which is 5-10 times of the total mass of the opening agent containing carbon-carbon double bond, the grafting monomer and the photoinitiator.

2. The modified opening agent according to claim 1, wherein The grafting monomer, the amount of which is 60-90% of the molar amount of carbon-carbon double bond contained in the opening agent in terms of the molar amount of mercapto contained.

3. The modified opening agent of claim 1, wherein, The photoinitiator, the amount of which is 2-4% of the molar amount of the grafting monomer.

4. The modified opening agent of claim 1, wherein, The solvent, the amount of which is 6-9 times of the total mass of the opening agent containing carbon-carbon double bond, the grafting monomer and the photoinitiator.

5. The modified opening agent of claim 1, wherein, The monomer containing mercapto and two or more hydroxyl or carboxyl is selected from mercapto compounds containing 2-4 hydroxyl or carboxyl.

6. The modified opening agent of claim 5, wherein, The monomer containing mercapto and two or more hydroxyl or carboxyl is selected from one or more of thiomalic acid, cis-1-(3-mercapto-1-oxopropyl)-2,5-piperidinedicarboxylic acid.

7. The modified opening agent of claim 1, wherein, The opening agent containing carbon-carbon double bond is selected from one or more of erucic acid amide, oleic acid amide; The photoinitiator is selected from one or more of ketone photoinitiators; The solvent is selected from amides.

8. The modified opening agent of claim 7, wherein, The photoinitiator is selected from one or more of 2,2-dimethoxy-2-phenylacetophenone, benzophenone.

9. The modified opening agent of claim 7, wherein, The solvent is N,N-dimethylformamide.

10. A process for the preparation of the modified pore opener according to any one of claims 1 to 9, characterized by the steps of It includes: (1) mixing the opening agent containing carbon-carbon double bond, the grafting monomer, the photoinitiator and the solvent, stirring until completely dissolved to obtain a solution; (2) placing the solution of step (1) under the condition of ultraviolet light irradiation in a nitrogen environment, stirring to carry out the reaction, then washing and drying to obtain the modified opening agent.

11. The method of claim 10, wherein, In step (1), the stirring temperature is 10-40℃, and the stirring speed is 50-200 rpm; In step (2), the ultraviolet light irradiation has a power of 36-72 W and a wavelength of 200-360 nm; In step (2), the reaction is carried out at a temperature of 10-40℃ for 10-30 min; The stirring speed is 50-200 rpm.

12. The method of claim 11, wherein, In step (1), the stirring temperature is 20-35℃, and the stirring speed is 60-150 rpm.

13. The preparation method according to claim 11, characterized in that, In step (2), the ultraviolet light wavelength is 250-350 nm.

14. The method of claim 11, wherein, In step (2), the reaction is carried out at a temperature of 20-35℃ for 15-25 min; 15. The method of claim 11, wherein, In step (2), the reaction is carried out at a stirring speed of 60-150 rpm.

16. Use of the modified opening agent of any one of claims 1-9 or the modified opening agent prepared by the method of any one of claims 10-15 in the field of modified biodegradable materials.

17. A print-modified biodegradable material, characterized in that, The raw materials comprise the modified opening agent according to any one of claims 1-9 or the modified opening agent prepared by the method according to any one of claims 10-15, and are prepared from raw materials comprising the following weight percentages: PBAT, 60-93%; PLA, 1-10%; modified opening agent, 0.2-1%; filler, 5-30%.

18. The printably modified biodegradable material according to claim 17, wherein, The raw materials comprise the modified opening agent according to any one of claims 1-9 or the modified opening agent prepared by the method according to any one of claims 10-15, and are prepared from raw materials comprising the following weight percentages: PBAT, 70-86%; PLA, 3-6%; modified opening agent, 0.3-0.6%; filler, 10-25%.

19. The printably modified biodegradable material of claim 17, wherein, The PBAT has a melt index of 1-5 g / 10 min in a test at 190°C under a load of 2.16 kg. The PLA has a melt index of 3-30 g / 10 min in a test at 190°C under a load of 2.16 kg. The filler is selected from one or more of talc and calcium carbonate.

20. The printably modified biodegradable material according to claim 19, wherein, The PLA has a melt index of 5-25 g / 10 min in a test at 190°C under a load of 2.16 kg.

21. A process for the preparation of the easily printable modified biodegradable material according to any one of claims 17-20, characterized in that, The method comprises the following steps: 1) mixing PBAT, PLA, modified opening agent and filler in a high-speed mixer; 2) extruding and granulating the mixture obtained in step 1) through a twin-screw extruder to obtain the easily-printable modified biodegradable material.

22. The method of claim 21, wherein, In step 1), the mixing conditions of the high-speed mixer are as follows: temperature 10-40°C, rotation speed 50-400 rpm, and mixing time 3-8 min. In step 2), the operating conditions of the twin-screw extruder are as follows: screw temperature 150-190°C, and rotation speed 150-500 rpm.

23. The preparation method according to claim 22, characterized in that, In step 1), the rotation speed is 100-300 rpm, and the mixing time is 4-7 min.

24. The method of claim 22, wherein, In step 2), the screw temperature is 160-180°C, and the rotation speed is 200-400 rpm.

Images