Environment-friendly low-fog PVC paste resin and preparation method thereof

Abstract

The invention discloses environment-friendly low-fog PVC paste resin and a preparation method thereof, and relates to the technical field of polymer chemical industry. The environment-friendly low-fog PVC paste resin is prepared from the following raw materials in parts by weight: 100 parts of a vinyl chloride monomer, 0.5 to 1.8 parts of a compound emulsifier, 0.005 to 0.10 part of an oil-soluble initiator and 90 to 150 parts of deionized water, wherein the compound emulsifier comprises an anionic surfactant and a co-emulsifier, and the weight of the anionic surfactant accounts for 30-60% of the total weight of the compound emulsifier; the anionic surfactant comprises a Gemini type anionic surfactant and a non-Gemini type anionic surfactant, and the weight of the Gemini type anionic surfactant accounts for 5%-35% of the total weight of the anionic surfactant. The preparation method is a micro-suspension polymerization method. The average polymerization degree of the obtained paste resin product is 1000-2500, the paste viscosity is 1000-5000 mPa.s, the atomization value is smaller than or equal to 5 mg, and the paste resin product has the advantages of being good in comprehensive performance, environmentally friendly, low in atomization and high in transparency.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer chemical engineering, and particularly relates to an environmentally friendly low-fog PVC paste resin and a preparation method thereof. Background Art

[0002] Polyvinyl chloride (PVC) paste resin is a unique liquid form of polyvinyl chloride resin. Polyvinyl chloride plasticizer paste can obtain polyvinyl chloride plastic products through a heating process. Because of its advantages such as low-cost processing equipment, simple and inexpensive molds, can be made into special shapes, and few heating times of products, it is widely used in processing such as coating, calendering, dipping, and rotational molding, and is the main raw material for leather, tarpaulin, wallpaper, automotive interiors, disposable PVC examination gloves, etc.

[0003] Compared with ordinary consumer leather, automotive leather has higher environmental protection requirements. Major automobile companies have successively put forward limit requirements for the fogging value of automotive materials to avoid the deterioration of the driving environment and safety. Enterprises such as automotive leather, floor mats, and interiors require PVC paste resin raw materials to have matching application performance. Therefore, it is the general trend to develop PVC paste resins with high transparency and low fogging. However, there is little relevant research in the existing technology. Most of them endow the products with low fogging performance by adding low-fogging environmental protection additives in the post-processing application field of PVC paste resin. However, since the problem has not been fundamentally solved, it is difficult to reach the limit value in the automotive field. Summary of the Invention

[0004] The present invention aims to solve at least one of the technical problems existing in the prior art or related technologies.

[0005] To this end, in the first aspect of the present invention, an environmentally friendly low-fog PVC paste resin is provided, and its raw material composition includes by weight:

[0006] 100 parts of vinyl chloride monomer,

[0007] 0.5 - 1.8 parts of composite emulsifier,

[0008] 0.005 - 0.10 parts of oil-soluble initiator,

[0009] 90 - 150 parts of deionized water;

[0010] Wherein, the composite emulsifier includes an anionic surfactant and a co-emulsifier, and the weight of the anionic surfactant accounts for 30% - 60% of the total weight of the composite emulsifier;

[0011] The anionic surfactant includes Gemini anionic surfactant and non-Gemini anionic surfactant, and the weight of the Gemini anionic surfactant accounts for 5% - 35% of the total weight of the anionic surfactant.

[0012] Furthermore, the non-Gemini anionic surfactant is selected from one or more of sodium dodecyl sulfonate, sodium dodecyl benzene sulfonate, sodium tetradecyl benzene sulfonate, sodium octyl sulfosuccinate, and secondary alkyl sulfonate.

[0013] Furthermore, the Gemini anionic surfactant is selected from sodium alkyl diphenyl methane disulfonate or / and sodium alkyl diphenyl ether disulfonate.

[0014] More specifically, the Gemini anionic surfactant is one or more of sodium mono-dodecyl diphenyl methane disulfonate, sodium bis-dodecyl diphenyl methane disulfonate, sodium mono-tetradecyl diphenyl methane disulfonate, sodium bis-tetradecyl diphenyl methane disulfonate, sodium mono-dodecyl diphenyl ether disulfonate, sodium bis-dodecyl diphenyl ether disulfonate, sodium mono-hexadecyl diphenyl ether disulfonate, and sodium bis-hexadecyl diphenyl ether disulfonate.

[0015] Furthermore, the co-emulsifier is selected from one or more of alkanes with carbon atom number ≥16, alcohols with carbon atom number ≥16, and acids with carbon atom number ≥16.

[0016] More specifically, the co-emulsifier is one or more of octadecanol, n-hexadecane, octadecanoic acid, and nonadecanoic acid.

[0017] Furthermore, the oil-soluble initiator is selected from one or more of azodiisobutyronitrile, azodiisooctanenitrile, cumyl peroxyneodecanoate, bis(2-ethylhexyl) peroxydicarbonate, and diisopropyl peroxydicarbonate.

[0018] Furthermore, the environmentally friendly low-fog PVC paste resin has an average degree of polymerization of 1000 - 2500, a paste viscosity of 1000 mPa·s - 5000 mPa·s, an atomization value ≤5 mg, a haze ≤16%, and a tensile strength ≥18 MPa.

[0019] In the second aspect of the present invention, a preparation method of the above-mentioned environmentally friendly low-fog PVC paste resin is provided, including: mixing the vinyl chloride monomer, the composite emulsifier, the oil-soluble initiator, and the deionized water in proportion and feeding them into a dispersion tank, then adding them into a polymerization kettle that has been vacuum deoxygenated while dispersing through a dispersion pump, so that the reaction raw materials form fine droplets of 0.1 μm - 2 μm; after filling the polymerization kettle with high-purity nitrogen to increase the pressure by 0.05 MPa - 0.1 MPa, heating the polymerization kettle for polymerization, and obtaining a polymerization latex through the polymerization reaction, filtering the polymerization latex and then performing spray drying and pulverization to obtain the environmentally friendly low-fog PVC paste resin.

[0020] Furthermore, for the polymerization reaction, the reaction temperature is 45°C - 55°C, and the reaction time is 12 h - 16 h.

[0021] Compared with the prior art, the present invention has at least the following beneficial effects:

[0022] For the environmentally friendly low-fog polyvinyl chloride paste resin provided by the present invention, due to the selection of an environmentally friendly and low-atomization-value composite emulsifier, and the anionic surfactants in the composite emulsifier include Gemini-type anionic surfactants and non-Gemini-type anionic surfactants, by controlling the weight ratio of the anionic surfactant in the composite emulsifier and the weight ratio of the Gemini-type anionic surfactant and the non-Gemini-type anionic surfactant, the PVC paste resin product has the properties of low VOC, low atomization value and high transparency. The average degree of polymerization of the PVC paste resin product prepared by the microsuspension polymerization method is 1000-2500, the paste viscosity is 1000 mPa·s-5000 mPa·s, the atomization value ≤ 5 mg, the haze ≤ 16%, and the tensile strength ≥ 18 MPa. It has the advantages of good comprehensive performance, environmental protection, low atomization and high transparency. Detailed implementation mode

[0023] By reading the following detailed description of the preferred implementation modes, various other advantages and benefits will become clear to those of ordinary skill in the art.

[0024] In the first aspect of the embodiments of the present invention, an environmentally friendly low-fog PVC paste resin is provided, and its raw material composition includes by weight:

[0025] 100 parts of vinyl chloride monomer,

[0026] 0.5-1.8 parts of composite emulsifier,

[0027] 0.005-0.10 parts of oil-soluble initiator,

[0028] 90-150 parts of deionized water;

[0029] Among them, the composite emulsifier includes an anionic surfactant and a co-emulsifier. The weight of the anionic surfactant accounts for 30%-60% of the total weight of the composite emulsifier. Preferably, the weight of the anionic surfactant accounts for 40%-55% of the total weight of the composite emulsifier.

[0030] The anionic surfactant includes Gemini-type anionic surfactant and non-Gemini-type anionic surfactant, and the weight of the Gemini-type anionic surfactant accounts for 5%-35% of the total weight of the anionic surfactant. Preferably, the weight of the Gemini-type anionic surfactant accounts for 10%-25% of the total weight of the anionic surfactant.

[0031] An embodiment of the present invention provides an environmentally friendly low-fog PVC paste resin, which is prepared by a micro-suspension polymerization method from raw materials of vinyl chloride monomer, a composite emulsifier, an oil-soluble initiator, and deionized water according to the above weight ratio. Among them, the composite emulsifier is composed of an anionic surfactant and a co-emulsifier. If the content of the anionic surfactant is too low, the dispersibility of the polymerization system will decrease and the reaction will be uneven; the polymerization reaction environment will deteriorate, easily leading to the aggregation of latex particles; if the content of the co-emulsifier is too low, the emulsification effect will be poor and the emulsion stability will deteriorate. Therefore, the ratio of the anionic surfactant to the co-emulsifier is crucial for the emulsion stability and the polymerization reaction. Experiments show that when the content of the anionic surfactant is controlled at 30% - 60% (preferably 40% - 55%), good dispersibility and reaction uniformity can be ensured; when the content of the co-emulsifier is controlled at 40% - 70% (preferably 45% - 60%), good emulsification effect and emulsion stability can be ensured; an imbalance in the ratio of the two will lead to the aggregation of latex particles, uneven reaction or poor emulsion stability, affecting the performance of the final product.

[0032] Gemini-type anionic surfactants have excellent properties of providing high surface activity at very low concentrations. However, if their content is too high, micelle nucleation is likely to occur, resulting in the generation of small latex particles, and these small latex particles are unstable in the system and easily aggregate into clusters, which is not conducive to the stability of the entire latex system. Experiments have found that when the weight of the Gemini-type anionic surfactant accounts for 5% - 35% (preferably 10% - 25%) of the total weight of the anionic surfactant, the latex system is stable and reliable.

[0033] Optionally, the non-Gemini-type anionic surfactant is selected from one or more of sodium dodecyl sulfonate, sodium dodecyl benzene sulfonate, sodium tetradecyl benzene sulfonate, sodium octyl sulfosuccinate, and secondary alkyl sulfonate.

[0034] Optionally, the Gemini-type anionic surfactant is selected from sodium alkyl diphenylmethane disulfonate or / and sodium alkyl diphenyl ether disulfonate. Preferably, the Gemini-type anionic surfactant is one or more of sodium monododecyl diphenylmethane disulfonate, sodium didodecyl diphenylmethane disulfonate, sodium monotetradecyl diphenylmethane disulfonate, sodium ditetradecyl diphenylmethane disulfonate, sodium monododecyl diphenyl ether disulfonate, sodium didodecyl diphenyl ether disulfonate, sodium monohexadecyl diphenyl ether disulfonate, and sodium dihexadecyl diphenyl ether disulfonate.

[0035] Optionally, the co-emulsifier is selected from one or more of alkanes with carbon atoms ≥ 16, alcohols with carbon atoms ≥ 16, and acids with carbon atoms ≥ 16. Further, the co-emulsifier is one or more of octadecanol, n-hexadecane, octadecanoic acid, and nonadecanoic acid.

[0036] Optionally, the oil-soluble initiator is selected from one or more of azobisisobutyronitrile (AIBN), azobisisoheptonitrile (ABVN), cumyl peroxyneodecanoate (CPND), bis(2-ethylhexyl) peroxydicarbonate (EHP), diisopropyl peroxydicarbonate (IPP).

[0037] In the second aspect of the embodiments of the present invention, there is provided a method for preparing the above-mentioned environmentally friendly low-fog PVC paste resin, including:

[0038] Mix vinyl chloride monomer, composite emulsifier, oil-soluble initiator and deionized water in proportion and feed them into a dispersion tank, then add them into a polymerization kettle that has completed vacuum deoxidation while dispersing through a dispersion pump, so that the reaction raw materials form fine droplets of 0.1 μm to 2 μm; after filling the polymerization kettle with high-purity nitrogen to increase the pressure by 0.05 MPa - 0.1 MPa, heat up the polymerization kettle for polymerization, and obtain a polymerization latex through the polymerization reaction; recover the unreacted vinyl chloride monomer; filter the polymerization latex and then perform spray drying and pulverization to obtain the environmentally friendly low-fog PVC paste resin. Optionally, the polymerization reaction temperature is 45°C to 55°C, and the reaction time is 12 h to 16 h.

[0039] Using the above micro-suspension polymerization method to prepare the environmentally friendly low-fog PVC paste resin, its average degree of polymerization is 1000 - 2500, the paste viscosity formed after mixing the environmentally friendly low-fog PVC paste resin and a plasticizer is 1000 mPa·s - 5000 mPa·s, the atomization value of the PVC paste resin product is ≤5 mg, the haze is ≤16%, and the tensile strength is ≥18 MPa.

[0040] Example 1 An environmentally friendly low-fog PVC paste resin and its preparation method

[0041] (I) Raw material composition and mass ratio

[0042] 100 parts of vinyl chloride monomer;

[0043] 1.277 parts of composite emulsifier, including an anionic surfactant and a co-emulsifier. The weight of the anionic surfactant accounts for 52.23% of the total weight of the composite emulsifier; among them, the anionic surfactant: 0.60 part of sodium dodecylbenzenesulfonate (non-Gemini type), 0.067 part of bis(dodecyldiphenylmethane) disulfonate (Gemini type); the weight of the Gemini type anionic surfactant accounts for 10.04% of the total weight of the anionic surfactant; co-emulsifier: 0.10 part of n-hexadecane, 0.51 part of stearic acid;

[0044] 0.0197 part of oil-soluble initiator, among which 0.013 part of ABVN and 0.0067 part of CPND;

[0045] 100 parts of deionized water.

[0046] (II) Preparation method

[0047] The polyvinyl chloride paste resin is prepared by micro - suspension polymerization. Specifically: the above - mentioned raw materials are mixed in proportion, fed into a dispersion tank, and added to a polymerization kettle with vacuum deoxidation through a dispersion pump while dispersing within 70 minutes, and polymerized to form liquid droplets with a particle size of 0.1 - 2 μm. High - purity nitrogen is filled into the polymerization kettle containing the reaction raw materials to increase the pressure in the polymerization kettle by 0.05 - 0.1 MPa, the reaction temperature is 55 °C, and the polymerization reaction is carried out for 13.5 h to obtain a polymerization latex. The unreacted monomers are recovered, and the polymerization latex is filtered, then spray - dried and pulverized and packaged to obtain the polyvinyl chloride paste resin.

[0048] Example 2: An environmentally friendly low - fog PVC paste resin and its preparation method

[0049] (I) Raw material composition and mass ratio

[0050] 100 parts of vinyl chloride monomer;

[0051] 0.55 parts of a composite emulsifier, including an anionic surfactant and a co - emulsifier. The weight of the anionic surfactant accounts for 38.18% of the total weight of the composite emulsifier; among them, anionic surfactant: (non - Gemini type) 0.199 parts of sodium dodecylbenzenesulfonate, 0.011 parts of bis - hexadecyl diphenyl ether disulfonate (Gemini type); the weight of the Gemini - type anionic surfactant accounts for 5.24% of the total weight of the anionic surfactant; co - emulsifier: 0.335 parts of nonadecanoic acid, 0.005 parts of octadecanol;

[0052] 0.013 parts of oil - soluble initiator ABVN;

[0053] 150 parts of deionized water.

[0054] (II) Preparation method

[0055] The polyvinyl chloride paste resin is prepared by micro - suspension polymerization. Specifically: the above - mentioned raw materials are mixed in proportion, fed into a dispersion tank, and added to a polymerization kettle with vacuum deoxidation through a dispersion pump while dispersing within 70 minutes, and polymerized to form liquid droplets with a particle size of 0.1 - 2 μm. High - purity nitrogen is filled into the polymerization kettle containing the reaction raw materials to increase the pressure in the polymerization kettle by 0.05 - 0.1 MPa, the reaction temperature is 48 °C, and the polymerization reaction is carried out for 15.2 h to obtain a polymerization latex. The unreacted monomers are recovered, and the polymerization latex is filtered, then spray - dried and pulverized and packaged to obtain the polyvinyl chloride paste resin.

[0056] Example 3: An environmentally friendly low - fog PVC paste resin and its preparation method

[0057] (I) Raw material composition and mass ratio

[0058] 100 parts of vinyl chloride monomer;

[0059] 1.7 parts of composite emulsifier, including an anionic surfactant and a co-emulsifier. The weight of the anionic surfactant accounts for 57% of the total weight of the composite emulsifier. Among them, the anionic surfactant: 0.500 part of sodium tetradecylbenzenesulfonate (non-Gemini type), 0.198 part of sodium dodecylsulfonate (non-Gemini type), 0.071 part of ditetradecyldiphenylmethanedisulfonate (Gemini type), 0.200 part of monotetradecyldiphenylmethanedisulfonate (Gemini type); the weight of the Gemini type anionic surfactant accounts for 27.97% of the total weight of the anionic surfactant; the co-emulsifier: 0.731 part of stearic acid;

[0060] 0.01 part of oil-soluble initiator, including 0.009 part of ABVN and 0.001 part of IPP;

[0061] 90 parts of deionized water.

[0062] (II) Preparation method

[0063] The polyvinyl chloride paste resin is prepared by the micro-suspension polymerization method. Specifically, the above raw materials are mixed in proportion and fed into a dispersion tank, and then added to a polymerization kettle with vacuum deoxidation while dispersing through a dispersion pump within 70 minutes to form droplets with a particle size of 0.1 - 2 μm. High-purity nitrogen is filled into the polymerization kettle containing the reaction raw materials to increase the pressure in the polymerization kettle by 0.05 - 0.1 MPa, the reaction temperature is 45 °C, and the polymerization reaction is carried out for 16 h to obtain a polymerization latex. The unreacted monomer is recovered, and the polymerization latex is filtered, then spray-dried and pulverized for packaging to obtain the polyvinyl chloride paste resin.

[0064] Example 4 An environmentally friendly low-fog PVC paste resin and its preparation method

[0065] (I) Raw material composition and mass ratio

[0066] 100 parts of vinyl chloride monomer;

[0067] 1.196 parts of composite emulsifier, including an anionic surfactant and a co-emulsifier. The weight of the anionic surfactant accounts for 52.34% of the total weight of the composite emulsifier. Among them, the anionic surfactant: 0.28 part of sodium tetradecylbenzenesulfonate (non-Gemini type), 0.28 part of sodium octylsulfosuccinate (non-Gemini type), 0.006 part of didodecyldiphenylether disulfonate (Gemini type), 0.060 part of monododecyldiphenylether disulfonate (Gemini type); the weight of the Gemini type anionic surfactant accounts for 10.54% of the total weight of the anionic surfactant; the co-emulsifier: 0.08 part of n-hexadecane, 0.49 part of stearic acid,

[0068] 0.024 parts of oil-soluble initiator, including 0.004 parts of AIBN and 0.02 parts of EHP;

[0069] 120 parts of deionized water.

[0070] (II) Preparation method

[0071] The polyvinyl chloride paste resin is prepared by micro-suspension polymerization. Specifically, the above raw materials are mixed in proportion and fed into a dispersion tank. They are added to a vacuum-deoxygenated polymerization kettle while being dispersed by a dispersion pump within 70 minutes to form liquid droplets with a particle size of 0.1 - 2 μm. High-purity nitrogen is filled into the polymerization kettle containing the reaction raw materials to increase the pressure in the polymerization kettle by 0.05 - 0.1 MPa. The reaction temperature is 50 °C, and the polymerization reaction lasts for 15.6 h to obtain a polymerization latex. The unreacted monomers are recovered, and the polymerization latex is filtered, then spray-dried and pulverized for packaging to obtain the polyvinyl chloride paste resin.

[0072] Example 5: An environmentally friendly low-fog PVC paste resin and its preparation method

[0073] (I) Raw material composition and mass ratio

[0074] 100 parts of vinyl chloride monomer;

[0075] 1.356 parts of composite emulsifier, including an anionic surfactant and a co-emulsifier. The weight of the anionic surfactant accounts for 52.06% of the total weight of the composite emulsifier. Among them, the anionic surfactant: 0.21 parts of sodium dodecyl sulfonate (non-Gemini type), 0.40 parts of sodium dodecyl benzene sulfonate (non-Gemini type), 0.096 parts of mono-dodecyl diphenyl ether disulfonate (Gemini type); the weight of the Gemini type anionic surfactant accounts for 13.60% of the total weight of the anionic surfactant; the co-emulsifier: 0.10 parts of n-hexadecane, 0.55 parts of nonadecanoic acid;

[0076] 0.028 parts of oil-soluble initiator, including 0.022 parts of ABVN and 0.006 parts of EHP;

[0077] 95 parts of deionized water.

[0078] (II) Preparation method

[0079] The polyvinyl chloride paste resin is prepared by micro-suspension polymerization, specifically as follows: The above raw materials are mixed in proportion and fed into a dispersion tank, and then added to a vacuum-deoxygenated polymerization kettle through a dispersion pump while dispersing within 70 minutes to form droplets with a particle size of 0.1 - 2 μm. High-purity nitrogen is filled into the polymerization kettle containing the reaction raw materials to increase the pressure in the polymerization kettle by 0.05 - 0.1 MPa, the reaction temperature is 50 °C, and the polymerization reaction is carried out for 15.0 h to obtain a polymerization latex. The unreacted monomers are recovered, and the polymerization latex is filtered, then spray-dried, pulverized and packaged to obtain the polyvinyl chloride paste resin.

[0080] Example 6 An environmentally friendly low-fog PVC paste resin and its preparation method

[0081] (I) Raw material composition and mass ratio

[0082] 100 parts of vinyl chloride monomer;

[0083] 1.121 parts of composite emulsifier, including an anionic surfactant and a co-emulsifier. The weight of the anionic surfactant accounts for 52.72% of the total weight of the composite emulsifier; among them, the anionic surfactant: 0.56 parts of sodium octyl sulfosuccinate (non-Gemini type), 0.031 parts of monododecyl diphenyl ether disulfonate (Gemini type); the weight of the Gemini type anionic surfactant accounts for 5.25% of the total weight of the anionic surfactant; the co-emulsifier: 0.53 parts of nonadecanoic acid;

[0084] 0.035 parts of oil-soluble initiator, including 0.005 parts of AIBN and 0.03 parts of EHP;

[0085] 120 parts of deionized water.

[0086] (II) Preparation method

[0087] The polyvinyl chloride paste resin is prepared by micro-suspension polymerization, specifically as follows: The above raw materials are mixed in proportion and fed into a dispersion tank, and then added to a vacuum-deoxygenated polymerization kettle through a dispersion pump while dispersing within 70 minutes to form droplets with a particle size of 0.1 - 2 μm. High-purity nitrogen is filled into the polymerization kettle containing the reaction raw materials to increase the pressure in the polymerization kettle by 0.05 - 0.1 MPa, the reaction temperature is 52 °C, and the polymerization reaction is carried out for 15.2 h to obtain a polymerization latex. The unreacted monomers are recovered, and the polymerization latex is filtered, then spray-dried, pulverized and packaged to obtain the polyvinyl chloride paste resin.

[0088] Example 7 An environmentally friendly low-fog PVC paste resin and its preparation method

[0089] (I) Raw material composition and mass ratio

[0090] 100 parts of vinyl chloride monomer;

[0091] 1.078 parts of compound emulsifier, including anionic surfactant and co-emulsifier. The weight of the anionic surfactant accounts for 50.83% of the total weight of the compound emulsifier. Among them, the anionic surfactant: 0.52 parts of sodium dodecylbenzenesulfonate (non-Gemini type), 0.004 parts of bis(hexadecyl) diphenyl ether disulfonate (Gemini type), 0.024 parts of mono(hexadecyl) diphenyl ether disulfonate (Gemini type); the weight of the Gemini type anionic surfactant accounts for 5.11% of the total weight of the anionic surfactant; the co-emulsifier: 0.53 parts of stearic acid;

[0092] 0.04 parts of oil-soluble initiator ABVN;

[0093] 130 parts of deionized water.

[0094] (II) Preparation method

[0095] The polyvinyl chloride paste resin is prepared by microsuspension polymerization. Specifically, the above raw materials are mixed in proportion and sent into a dispersion tank, and then added into a polymerization kettle with vacuum deoxidation while dispersing through a dispersion pump within 70 minutes to form droplets with a particle size of 0.1 - 2 μm. High-purity nitrogen is filled into the polymerization kettle containing the reaction raw materials to increase the pressure in the polymerization kettle by 0.05 - 0.1 MPa, the reaction temperature is 52 °C, and the polymerization reaction is carried out for 15.2 h to obtain a polymerization latex. The unreacted monomers are recovered, and the polymerization latex is filtered, then spray-dried and pulverized and packaged to obtain the polyvinyl chloride paste resin.

[0096] Comparative Example 1 A polyvinyl chloride paste resin

[0097] (I) Raw material composition and mass ratio

[0098] 100 parts of vinyl chloride monomer;

[0099] 1.277 parts of compound emulsifier, including anionic surfactant and co-emulsifier. The weight of the anionic surfactant accounts for 65.23% of the total weight of the compound emulsifier. Among them, the anionic surfactant: 0.766 parts of sodium dodecylbenzenesulfonate (non-Gemini type), 0.067 parts of mono(hexadecyl) diphenyl ether disulfonate (Gemini type); the weight of the Gemini type anionic surfactant accounts for 8.04% of the total weight of the anionic surfactant; the co-emulsifier: 0.10 parts of n-hexadecane, 0.344 parts of stearic acid;

[0100] 0.0197 parts of oil-soluble initiator, among which 0.013 parts of ABVN and 0.0067 parts of CPND,

[0101] 100 parts of deionized water.

[0102] (II) Preparation method

[0103] The polyvinyl chloride paste resin was prepared by microsuspension polymerization, which was the same as in Example 1.

[0104] Comparative Example 2: A polyvinyl chloride paste resin

[0105] (I) Raw material composition and quality ratio

[0106] A polyvinyl chloride paste resin, whose raw materials include, by weight:

[0107] 100 parts of vinyl chloride monomer;

[0108] 1.198 parts of a composite emulsifier, including an anionic surfactant and an auxiliary emulsifier, wherein the weight of the anionic surfactant accounts for 28.54% of the total weight of the composite emulsifier; wherein the anionic surfactant includes: 0.118 parts of sodium dodecyl sulfonate (non-Gemini type), 0.156 parts of sodium dodecylbenzene sulfonate (non-Gemini type), and 0.068 parts of sodium didodecyl diphenylmethane disulfonate (Gemini type); the weight of the Gemini type anionic surfactant accounts for 19.88% of the total weight of the anionic surfactant; the auxiliary emulsifier includes: 0.131 parts of n-hexadecane and 0.725 parts of nonadecanoic acid;

[0109] 0.028 parts of oil-soluble initiator, including 0.022 parts of ABVN and 0.006 parts of EHP;

[0110] 95 parts of deionized water.

[0111] (II) Preparation method

[0112] The polyvinyl chloride paste resin was prepared by microsuspension polymerization, which was the same as in Example 1.

[0113] Comparative Example 3: A polyvinyl chloride paste resin

[0114] (I) Raw material composition and quality ratio

[0115] A polyvinyl chloride paste resin, whose raw materials include, by weight:

[0116] 100 parts of vinyl chloride monomer;

[0117] 0.80 parts of composite emulsifier, including anionic surfactant and co-emulsifier, the weight of anionic surfactant accounts for 52.50% of the total weight of emulsifier; wherein, anionic surfactant: sodium octyl sulfonate succinate (non-Gemini type) 0.42 parts; co-emulsifier: octadecyl alcohol 0.3 parts, nonadecanoic acid 0.08 parts;

[0118] 0.025 parts of oil-soluble initiator, including 0.02 parts of AIBN and 0.005 parts of EHP;

[0119] 90 parts of deionized water.

[0120] (II) Preparation method

[0121] The polyvinyl chloride paste resin was prepared by microsuspension polymerization, which was the same as in Example 2.

[0122] Comparative Example 4: A polyvinyl chloride paste resin

[0123] (I) Raw material composition and quality ratio

[0124] A polyvinyl chloride paste resin, whose raw materials include, by weight:

[0125] 100 parts of vinyl chloride monomer;

[0126] 1.6 parts of composite emulsifier, including anionic surfactant and auxiliary emulsifier, the weight of anionic surfactant accounts for 52.5% of the total weight of emulsifier; wherein, anionic surfactant: sodium monododecyl diphenyl ether disulfonate (Gemini type) 0.84 parts; auxiliary emulsifier: n-hexadecane 0.76 parts;

[0127] Oil-soluble initiator ABVN0.038;

[0128] 90 parts of deionized water.

[0129] (II) Preparation method

[0130] The polyvinyl chloride paste resin was prepared by microsuspension polymerization, which was the same as in Example 3.

[0131] Results and Discussion

[0132] The performance of the environmentally friendly low-fog PVC paste resin products obtained in Examples 1-7 and Comparative Examples 1-4 is shown in Table 1. As can be seen from Table 1, the environmentally friendly low-fog PVC paste resins of Examples 1-7 have performance advantages such as low atomization value and good transparency compared with Comparative Examples 1-4. Among them, Comparative Example 1 has a large amount of anionic surfactants, and its own atomization value is slightly large, resulting in a large atomization value of the final product. Comparative Example 2 has an imbalance of osmotic pressure inside and outside the latex particles due to excessive co-emulsifiers, resulting in demulsification. Comparative Example 3 does not have a Gemini-type anionic surfactant in the anionic surfactant, and in order to improve the stability of the emulsification system, the amount of higher alcohol is increased. The atomization value of the higher alcohol itself is large, resulting in a large atomization value of the final product. Comparative Example 4 has only a Gemini-type anionic surfactant in the anionic surfactant, resulting in excessive small particles and instability, leading to explosion.

[0133] Table 1 Comparison of product indicators of Examples 1-7 and Comparative Examples 1-4

[0134]

[0135] It is easily understandable to those skilled in the art that, on the premise of no conflict, the above-mentioned advantageous ways can be freely combined and superimposed. The above are only the preferred embodiments of the present application and are not intended to limit the present application. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present application shall be included within the protection scope of the present application. The above is only the preferred implementation manner of the present application. It should be noted that for those of ordinary skill in the art in this technical field, several improvements and variations can be made without departing from the technical principle of the present application, and these improvements and variations should also be regarded as within the protection scope of the present application.

Claims

1. An environmentally friendly low-fog PVC paste resin, characterized in that, Its raw material composition includes by weight parts: 100 parts of vinyl chloride monomer, 0.5 - 1.8 parts of composite emulsifier, 0.005 - 0.10 parts of oil-soluble initiator, 90 - 150 parts of deionized water; Among them, the composite emulsifier includes an anionic surfactant and a co-emulsifier, and the weight of the anionic surfactant accounts for 30% - 60% of the total weight of the composite emulsifier; The anionic surfactant includes Gemini-type anionic surfactant and non-Gemini-type anionic surfactant, and the weight of the Gemini-type anionic surfactant accounts for 5% - 35% of the total weight of the anionic surfactant.

2. The environmentally friendly low-fog PVC paste resin according to claim 1, characterized in that, The non-Gemini-type anionic surfactant is selected from one or more of sodium dodecyl sulfonate, sodium dodecyl benzene sulfonate, sodium tetradecyl benzene sulfonate, sodium octyl sulfosuccinate, secondary alkyl sulfonate.

3. The environmentally friendly low-fog PVC paste resin according to claim 1, characterized in that The Gemini-type anionic surfactant is selected from sodium alkyl diphenylmethane disulfonate or / and sodium alkyl diphenyl ether disulfonate.

4. The environmentally friendly low-fog PVC paste resin according to claim 3, characterized in that, The Gemini-type anionic surfactant is one or more of sodium mono-dodecyl diphenylmethane disulfonate, sodium bis-dodecyl diphenylmethane disulfonate, sodium mono-tetradecyl diphenylmethane disulfonate, sodium bis-tetradecyl diphenylmethane disulfonate, sodium mono-dodecyl diphenyl ether disulfonate, sodium bis-dodecyl diphenyl ether disulfonate, sodium mono-hexadecyl diphenyl ether disulfonate, sodium bis-hexadecyl diphenyl ether disulfonate.

5. The environmentally friendly low-fog PVC paste resin according to claim 1, characterized in that, The co-emulsifier is selected from one or more of alkanes with carbon atom number ≥16, alcohols with carbon atom number ≥16, acids with carbon atom number ≥16.

6. The environmentally friendly low-fog PVC paste resin according to claim 5, wherein, The co-emulsifier is one or more of octadecanol, n-hexadecane, stearic acid, nonadecanoic acid.

7. The environmentally friendly low-fog PVC paste resin according to claim 1, wherein The oil-soluble initiator is selected from one or more of azobisisobutyronitrile, azobisisoheptonitrile, cumyl peroxyneodecanoate, bis(2-ethylhexyl) peroxydicarbonate, diisopropyl peroxydicarbonate.

8. The environmentally friendly low-fog PVC paste resin according to any one of claims 1-7, characterized in that, The environmentally friendly low-fog PVC paste resin has an average degree of polymerization of 1000 - 2500, a paste viscosity of 1000 mPa·s - 5000 mPa·s, an atomization value ≤5 mg, a haze ≤16%, and a tensile strength ≥18 MPa.

9. A preparation method of an environment-friendly low-fog PVC paste resin, characterized in that, The preparation method of the environmentally friendly low-fog PVC paste resin according to any one of claims 1 - 7 includes: Mix the vinyl chloride monomer, the composite emulsifier, the oil-soluble initiator and the deionized water in proportion and send them into a dispersion tank, then add them into a polymerization kettle that has been vacuum deoxygenated while dispersing through a dispersion pump, so that the reaction raw materials form fine droplets of 0.1 μm - 2 μm; after charging high-purity nitrogen into the polymerization kettle to increase the pressure by 0.05 MPa - 0.1 MPa, heat up the polymerization kettle for polymerization, and obtain a polymerization latex through the polymerization reaction. Filter the polymerization latex and then carry out spray drying and pulverization to obtain the environmentally friendly low-fog PVC paste resin.

10. The preparation method of the environment-friendly low-fog PVC paste resin according to claim 9, characterized in that, For the polymerization reaction, the reaction temperature is 45°C - 55°C, and the reaction time is 12 h - 16 h.

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