WO2021008321A1 - 一种聚丙烯酸酯类聚合物复合材料及其制备方法 - Google Patents

一种聚丙烯酸酯类聚合物复合材料及其制备方法 Download PDF

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WO2021008321A1
WO2021008321A1 PCT/CN2020/098134 CN2020098134W WO2021008321A1 WO 2021008321 A1 WO2021008321 A1 WO 2021008321A1 CN 2020098134 W CN2020098134 W CN 2020098134W WO 2021008321 A1 WO2021008321 A1 WO 2021008321A1
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Prior art keywords
toughening agent
layer
shell structure
polyacrylate polymer
composite material
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English (en)
French (fr)
Inventor
戴建建
叶南飚
黄险波
唐磊
黄宝奎
何超雄
付锦锋
杨霄云
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Kingfa Science and Technology Co Ltd
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Kingfa Science and Technology Co Ltd
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Priority to JP2022501215A priority Critical patent/JP2022540212A/ja
Priority to EP20840005.1A priority patent/EP3998308A4/en
Priority to KR1020227001775A priority patent/KR102678133B1/ko
Priority to US17/626,126 priority patent/US20220275193A1/en
Publication of WO2021008321A1 publication Critical patent/WO2021008321A1/zh
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/08—Homopolymers or copolymers of acrylic acid esters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B11/00—Making preforms
    • B29B11/06—Making preforms by moulding the material
    • B29B11/10—Extrusion moulding
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3472—Five-membered rings
    • C08K5/3475—Five-membered rings condensed with carbocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/10—Homopolymers or copolymers of methacrylic acid esters
    • C08L33/12—Homopolymers or copolymers of methyl methacrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/10—Transparent films; Clear coatings; Transparent materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/22—Mixtures comprising a continuous polymer matrix in which are dispersed crosslinked particles of another polymer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/53—Core-shell polymer

Definitions

  • the invention relates to the technical field of polymer materials, in particular to a polyacrylate polymer composite material and a preparation method thereof.
  • PVC decorative materials have been widely used in interior architectural decoration to replace traditional ceramics, paint, and wood decoration.
  • PVC decorative materials are mainly made into films with various patterns, which are glued to the surfaces of walls, furniture, etc., to play a decorative and beautiful effect.
  • sunlight such as windows, balconies, doorways
  • PVC decorative film also has a very large application demand.
  • PVC itself has very poor weather resistance and is very easy to change color when used outdoors, which limits its application.
  • the film is made of UV blocking PMMA material, which is adhered to the PVC decorative film to make a composite film. Since the ultraviolet rays in the sunlight are partially blocked by the PMMA film, the PVC decorative film will not be irradiated by ultraviolet rays and change color, greatly improving its outdoor service life.
  • Polyacrylate polymers have the advantages of high transparency and high hardness.
  • PMMA polymethyl methacrylate
  • PMMA is a brittle material with great rigidity. When processed into a film, it is prone to breakage, which cannot meet the requirements of processing and use at all. Therefore, PMMA must be toughened.
  • Patent 200680048017.8 discloses a PMMA film with particularly high weather resistance and high UV protection. It uses an impact modifier with a two-layer or three-layer core-shell structure, and preferably uses an impact modifier with a two-layer core-shell structure.
  • the impact modifier with a two-layer core-shell structure has good toughness and transparency, it is easy to cause whitening when folded in half. To solve the problem of whitening, the particle size of the toughening agent must be reduced, but the toughening efficiency will be reduced, and it is difficult to ensure that the performance requirements for processing into a film are met.
  • the toughening agent is mainly composed of MAAS rubber and core-shell structure polymer (from seed emulsion butyl acrylate and from ethylene glycol dimethacrylate, allyl methacrylate).
  • the mixture of esters is composed of latex particles prepared by crosslinking agent.
  • the anti-folding whitening effect of the toughening agent is not satisfactory.
  • the purpose of the present invention is to provide a polyacrylate polymer composite material, which has the advantages of high transparency, high toughening efficiency, and a film prepared into a film that is repeatedly folded in half without breaking or whitening marks.
  • Another object of the present invention is to provide a method for preparing the above-mentioned polyacrylate polymer composite material.
  • a polyacrylate polymer composite material in parts by weight, comprising the following components:
  • the toughening agent is selected from the group consisting of a two-layer core-shell structure toughening agent and a three-layer core-shell structure toughening agent.
  • the two-layer core-shell structure toughening agent accounts for 10% of the total weight of the toughening agent. 45%.
  • the present invention has found through experiments that the toughening performance and the flexural whitening resistance are contradictory.
  • a certain kind of toughening agent has a large particle size and high toughening efficiency. When it is folded in half, it will cause more silver streaks or voids, and the whitening will be more obvious. In order to reduce the whitening, the particle size needs to be reduced, but the toughening efficiency will decrease. Therefore, in order to obtain a toughening agent with good toughening effect, high transparency and good anti-folding whitening effect, the present invention has been explored.
  • the toughening agent with a two-layer core-shell structure provides excellent toughening effect and good transparency, but it is easy to cause whitening.
  • the present invention finds that, compared with the two-layer core-shell structure toughening agent, the middle rubber layer of the three-layer core-shell structure toughening agent needs higher energy to make the rubber hollow, so it is more difficult to produce whitening .
  • Compounding three-layer core-shell structure toughening agent can improve the toughening efficiency, but the transparency of the three-layer core-shell structure toughening agent is slightly worse. Adding too much will have a greater impact on the transparency of the overall material. The ratio of the amount of the toughening agent to obtain the excellent transparency and the advantages of the film prepared by repeated folding in half will not break or whiten.
  • the shell layer of the two-layer core-shell structure toughening agent is polymethyl methacrylate, and the core layer is a cross-linked butyl acrylate and styrene copolymer; the three-layer core-shell structure toughening agent
  • the outer layer is polymethyl methacrylate
  • the middle rubber layer is cross-linked butyl acrylate and styrene copolymer
  • the inner layer is polymethyl methacrylate.
  • the shell layer of the two-layer core-shell structure toughening agent is polyacrylate, styrene-acrylonitrile-methyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-methyl methacrylate Ester copolymer etc.
  • the core layer is polybutyl acrylate, styrene-butadiene copolymer, silicone rubber, etc.
  • the outer layer of the three-layer core-shell structure toughening agent is polyacrylate, styrene-acrylonitrile-methyl methacrylate copolymer, styrene-acrylonitrile copolymer, styrene-methyl methacrylate Copolymers, etc.
  • the middle rubber layer is polybutyl acrylate, styrene-butadiene copolymer, silicone rubber, etc.
  • the inner layer is polyacrylate, styrene-acrylonitrile-methyl methacrylate copolymer, styrene -Acrylonitrile copolymer, styrene-methyl methacrylate copolymer, etc.
  • the shell layer accounts for 45-70% of the total weight of the two-layer core-shell structure toughening agent.
  • the middle rubber layer of the three-layer core-shell structure toughening agent accounts for 25-45% of the total weight of the three-layer core-shell structure toughening agent.
  • the above-mentioned preferred layer ratio is to improve the compatibility of the core-shell toughening agent in the polyacrylate polymer matrix, and to reduce the small voids caused by the displacement of the toughening agent and the resin matrix after bending. Fold white.
  • the two-layer core-shell structure toughening agent accounts for 20-35% of the total weight of the toughening agent.
  • the refractive index difference between the toughening agent and the polyacrylate polymer is less than 0.010.
  • the toughening agent is distributed in the resin matrix like an island, and the toughening agent and the matrix are directly connected to the transition surface. If the refractive index of the two substances is different, the light will be transmitted Therefore, the smaller the difference in refractive index between the toughening agent and the resin matrix, the higher the transparency.
  • the refractive index is generally about 1.49, and the refractive index of the toughening agent used at this time is close to this value.
  • the two-layer core-shell toughening agent is mainly polybutyl acrylate rubber. The core layer needs to adjust the refractive index to be consistent with the polymethyl methacrylate shell layer, which is 1.49.
  • the polyacrylate polymer is selected from polymethyl acrylate polymer, polyethyl acrylate polymer, polypropyl acrylate polymer, polybutyl acrylate polymer, polypentyl acrylate polymer At least one of them.
  • Polyacrylate polymers are mainly obtained by radical polymerization of acrylic compound monomers. Among them, it may be the copolymerization of multiple acrylic acid ester compound monomers.
  • polymethyl methacrylate (PMMA) can be a free radical homopolymerization of pure methyl methacrylate, or a mixture of methyl methacrylate and other acrylic compounds.
  • Other acrylate compounds can be methyl acrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, isobutyl methacrylate, pentyl methacrylate, 2-ethylhexyl methacrylate and the like.
  • weathering agents such as anti-ultraviolet agents can be added to prepare a high-transparency and high-flexibility anti-ultraviolet film.
  • the weathering agent is selected from benzotriazole
  • the ultraviolet absorber used has excellent thermal stability.
  • the benzotriazole ultraviolet absorber can be selected from 2-(2'-hydroxy-5'-methyl)-benzotriazole, 2-(3',5'-di-tert-butyl-2' -Hydroxy)-benzotriazole, 2-(2'-hydroxy-3'-isobutyl-5'-tert-butyl)-benzotriazole, 2-(2'-hydroxy-3',5' -Bis(1,1-Dimethylphenyl)-benzotriazole, 2-(2'-hydroxy-5'-tert-octyl)-benzotriazole, 2-(2'-hydroxy-3' -(1,1-Dimethylphenyl)-5'-[1,1,3,3-tetramethylbutyl]-benzotriazole, 2,2'methylene-(6-(2H -At least one of benzotriazole)-4-tert-octyl)phenol.
  • the HALS compound is selected from the group consisting of bis-2,2,6,6-tetramethylpiperidinol sebacate, N,N'-(2,2,6,6-tetramethyl, 4-amino piperidine (Pyridine)-isophthalamide, bis-1-octyloxy-2,2,6,6-tetramethylpiperidinol sebacate, methacrylic acid (1,2,2,6,6-pentamethyl At least one of piperidinol) esters.
  • auxiliary agents which are selected from at least heat stabilizers, antioxidants, anti-dripping agents, lubricants, and plasticizers.
  • auxiliary agents selected from at least heat stabilizers, antioxidants, anti-dripping agents, lubricants, and plasticizers.
  • the lubricant is metal stearate lubricant, alkyl stearate lubricant, pentaerythritol stearate lubricant, paraffin wax or montan wax.
  • the anti-dripping agent is selected from at least one of polytetrafluoroethylene, silicone-coated polytetrafluoroethylene, and methacrylate polymer-coated polytetrafluoroethylene.
  • the heat stabilizer is an organic phosphite, preferably triphenyl phosphite, tris-(2,6-dimethylphenyl) phosphite, tri-nonylphenyl phosphite, dimethylbenzene Phosphonate or trimethyl phosphate.
  • the antioxidant is organic phosphite, alkylated monohydric phenol or polyhydric phenol, alkylation reaction product of polyphenol and diene, butylation reaction product of p-cresol or dicyclopentadiene, alkane Alkylated hydroquinones, hydroxylated thiodiphenyl ethers, alkylene-bisphenols, benzyl compounds or polyol ester antioxidants.
  • the plasticizer is phthalate.
  • the preparation method of polyacrylate polymer composite material includes the following steps: weigh the components according to the proportion, put the polyacrylate polymer, toughening agent, and weathering agent into a high-speed mixer to mix evenly, and then pass
  • the extruder is extruded and granulated (the screw speed is 300-500rpm, and the temperature of each section of the extruder is set to 80-100°C in the first zone, 160-180°C in the second zone, and 160-180°C in the third zone from the feeding port to the head.
  • the particle size of the toughening agent is 50-250nm
  • the particle size of the toughening agent is 130-170 nm. Observed by scanning electron microscope, the toughening agent will be distributed in small islands in the resin matrix. The particle size distribution of the toughening agent is normally distributed. The peak of the particle size distribution of the toughening agent is within the above particle size range. The transparency of the composite material And the whitening resistance is satisfactory, and the toughening efficiency can be maintained at a high level.
  • the application of the above-mentioned polyacrylate polymer composite material is used for blocking ultraviolet film or coating.
  • the present invention has the following beneficial effects
  • the present invention mainly selects the combination of a specific two-layer core-shell structure toughening agent and a specific three-layer core-shell structure toughening agent to further reduce the difference in refractive index between the toughening agent and the resin matrix, and through Adjusting the dosage ratio of the two toughening agents to obtain excellent transparency and the advantages of preparing a film that is repeatedly folded in half without breaking or whitening marks make the polyacrylate polymer composite material have good transparency and anti-folding whitening effect, and Good toughening effect. It can be prepared as a film with high light transmittance, good toughness, and no white folding after repeated folding in half, and has a wide range of applications.
  • the raw materials used in the present invention are all derived from commercially available products.
  • PMMA The weight average molecular weight is 130,000 g/mol, and the refractive index is 1.49;
  • Two-layer core-shell structure toughening agent A The shell layer is polymethyl methacrylate, the core layer is a cross-linked butyl acrylate and styrene copolymer, and the shell layer accounts for the total weight of the two-layer core-shell structure toughening agent 61%, refractive index 1.495, particle size distribution between 50-200nm;
  • Two-layer core-shell structure toughening agent B The shell layer is polymethyl methacrylate, the core layer is a cross-linked butyl acrylate and styrene copolymer, and the shell layer accounts for the total weight of the two-layer core-shell structure toughening agent 75%, refractive index 1.480, particle size distribution between 50-200nm;
  • Two-layer core-shell structure toughener C The shell layer is polymethyl methacrylate, the core layer is styrene-butadiene copolymer, and the shell layer accounts for 61% of the total weight of the two-layer core-shell structure toughener , Refractive index is 1.931, particle size distribution is between 50-200nm;
  • Three-layer core-shell structure toughening agent A the outer layer is polymethyl methacrylate, the middle rubber layer is cross-linked butyl acrylate and styrene copolymer, the inner layer is polymethyl methacrylate, the middle rubber layer It accounts for 41% of the total weight of the three-layer core-shell structure toughening agent, the refractive index is 1.488, and the particle size distribution is between 50-200nm;
  • Three-layer core-shell structure toughener B the outer layer is polymethyl methacrylate, the middle rubber layer is cross-linked butyl acrylate and styrene copolymer, the inner layer is polymethyl methacrylate, the middle rubber layer It accounts for 20% of the total weight of the three-layer core-shell structure toughening agent, the refractive index is 1.479, and the particle size distribution is between 50-200nm;
  • Three-layer core-shell structure toughening agent C the outer layer is polymethyl methacrylate, the middle rubber layer is silicone rubber, the inner layer is polymethyl methacrylate, and the middle rubber layer occupies a three-layer core-shell structure 41% of the total weight of the agent, refractive index 1.508, particle size distribution between 50-200nm;
  • Antioxidant Tetra [ ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid] pentaerythritol ester and tris [2.4-di-tert-butyl phenyl] phosphite compound;
  • Lubricant ethylene bis-stearamide.
  • Weathering agent TINUVIN 770DF, HALS compound, bis-2,2,6,6-tetramethylpiperidinol sebacate;
  • the preparation method of the polyacrylate polymer composite material of the embodiment and the comparative example Weigh the components according to the proportion, and put the polyacrylate polymer, toughening agent, weathering agent, antioxidant and lubricant into high-speed mixing Mix uniformly in the feeder, and then extrude and granulate through the extruder (the screw speed is 300-500rpm, the temperature of each section of the extruder is set to 80-100°C in the first zone and 80-100 in the second zone from the feeding port to the head 160-180°C, three-zone temperature 190-210°C, four-zone temperature 190-210°C, five-zone temperature 190-210°C, six-zone temperature 180-200°C, seven-zone temperature 180-200°C, eight-zone temperature 190- 210°C, nine-zone temperature 190-210°C, head temperature 200-220°C) to obtain polyacrylate polymer composite material.
  • the screw speed is 300-500rpm
  • the temperature of each section of the extruder is set to 80
  • Notched impact strength of cantilever beam Tested in accordance with the standard of GB1843-1996 "Plastic Cantilever Beam Impact Test Method", the pendulum energy is 2.75J, and the test is at room temperature.
  • Anti-folding whitening make a 60um thick film, and observe the whitening of the film by folding the film in half.
  • the severity level is classified as: none, mild, obvious, and severe.
  • Table 1 The distribution ratio (parts by weight) of each group of the embodiment and the results of each performance test
  • Table 2 The distribution ratio (weight parts) of each group of the comparative example and the performance test results
  • Example 2/5/6/7 It can be seen from Example 2/5/6/7 that the compounding ratio of the double-layer and three-layer core-shell structure toughening agent is critical under the same amount of toughening agent. Under the optimal compounding ratio, The comprehensive performance of mechanical properties, transparency and anti-folding whitening is better, which is more conducive to popularization and application.
  • Example 2/8 It can be seen from Example 2/8 that the structure ratio of the second-selected double-layer and triple-layer core-shell structure toughening agent can seriously affect the transparency.
  • Comparative Example 1 It can be seen from Comparative Example 1 that not all the composites of double-layer and triple-layer core-shell structure toughening agents can obtain excellent transparency, mechanical properties, and anti-whitening properties.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
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  • Engineering & Computer Science (AREA)
  • Graft Or Block Polymers (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Processing And Handling Of Plastics And Other Materials For Molding In General (AREA)

Abstract

本发明公开了一种聚丙烯酸酯类聚合物复合材料，其特征在于，按重量份计，包括以下组分：聚丙烯酸酯类聚合物100份；增韧剂15-100份；所述的增韧剂选自两层核-壳结构增韧剂和三层核-壳结构增韧剂的复配，两层核-壳结构增韧剂占增韧剂总重量份的10-45％。上述聚丙烯酸酯类聚合物复合材料具有透明度高、增韧效率高，并且制备成薄膜反复对折不会断裂也无折白痕迹。

Description

一种聚丙烯酸酯类聚合物复合材料及其制备方法 技术领域
本发明涉及高分子材料技术领域，特别是涉及一种聚丙烯酸酯类聚合物复合材料及其制备方法。
背景技术
近些年，PVC装饰材料被大量应用于室内建筑装饰，替代传统陶瓷、油漆、木质装饰。PVC装饰材料主要是制成各种图案的薄膜，粘在墙面、家具等表面，起装饰美观效果。但是，在室内长期使用时，在靠窗户、阳台、门口等受到太阳光照射的地方，会出现变色，并且表面容易被划伤，影响美观。在室外墙面、园林景观等，PVC装饰膜也有非常大的应用需求。但PVC本身耐候性非常差，在户外使用非常容易变色，从而限制了其应用。选用紫外阻隔PMMA材料制成薄膜，粘附在PVC装饰膜上制成复合薄膜。由于太阳光中的紫外线部分被PMMA膜阻挡，因此PVC装饰膜将不受紫外线的照射而变色，大大提高其户外使用寿命。
聚丙烯酸酯类聚合物具有高透明性、硬度高等优点。尤其是聚甲基丙烯酸甲酯(PMMA)具有高透明性、高光泽、高表面硬度和优异的耐候性，被广泛应用于导光板、灯罩外壳、建筑有机玻璃、卫浴、汽车等。大量文献报道，PMMA是一种具有优异光稳定性的聚合物，非常适宜用于户外对耐候要求极高的场合。但PMMA为脆性材料，其刚性很大，在加工成薄膜时，很容易出现断裂现象，根本无法满足加工和使用要求。因此，必须对PMMA进行增韧。
专利200680048017.8公开了一种具有特别高耐气候性和较高紫外线防护作用的PMMA膜。其采用具有两层或三层的核-壳结构的冲击改性剂，优选使用两层核壳结构的冲击改性剂。但是两层核壳结构的冲击改性剂虽然具有良好的韧性和透明度，但是其在对折使容易引起折白。解决折白就必须减小增韧剂的粒径，但会降低增韧效率，难以保证满足加工成薄膜的性能要求。
中国专利201310155826.0公开了一种PMMA增韧剂，增韧剂主要是由MAAS橡胶和核壳结构聚合物(由种子乳液丙烯酸丁酯与由二甲基丙烯酸乙二醇酯、甲基丙烯酸烯丙醇酯的混合物为交联剂制得的乳胶粒子)组成。但是， 该增韧剂的抗折白效果不能令人满意。
发明内容
本发明的目的在于，提供一种聚丙烯酸酯类聚合物复合材料，具有透明度高，增韧效率高，并且制备成薄膜反复对折不会断裂也无折白痕迹的优点。
本发明的另一目的在于，提供上述聚丙烯酸酯类聚合物复合材料的制备方法。
本发明是通过以下技术方案实现的：
一种聚丙烯酸酯类聚合物复合材料，按重量份计，包括以下组分：
聚丙烯酸酯类聚合物   100份；
增韧剂               15-100份；
所述的增韧剂选自两层核-壳结构增韧剂和三层核-壳结构增韧剂的复配，两层核-壳结构增韧剂占增韧剂总重量份的10-45％。
本发明通过实验发现，增韧性能和抗折白性能是互相矛盾的。某一种增韧剂，粒径大增韧效率高，则其对折时引发银纹或空穴就多，折白就越明显。为了减少折白，需要减小粒径，但是增韧效率就会下降。因此，为了得到增韧效果好、透明度高、抗折白效果好的增韧剂，本发明进行了探索。两层核-壳结构的增韧剂提供了优秀的增韧效果，透明性也较好，但是容易引起折白。为了改善折白缺陷，就必须减小粒径，但是这样会导致增韧效率的降低。本发明发现，相比于两层核-壳结构的增韧剂，三层核-壳结构增韧剂的中间橡胶层需要更高的能量才能使橡胶发生空洞化，因此会更难产生折白。复配三层核-壳结构增韧剂能够提高增韧效率，但是三层核-壳结构增韧剂的透明性略差，加入过多会对整体材料的透明性影响较大，通过调节两种增韧剂的用量比来得到优良的透明度以及制备成薄膜反复对折不会断裂也无折白痕迹的优点。
所述的两层核-壳结构增韧剂的壳层为聚甲基丙烯酸甲酯，核层为交联的丙烯酸丁酯与苯乙烯共聚物；所述的三层核-壳结构增韧剂的外层为聚甲基丙烯酸甲酯，中间橡胶层为交联的丙烯酸丁酯与苯乙烯共聚物，里层为聚甲基丙烯酸甲酯。
一般的，两层核-壳结构增韧剂的壳层为聚丙烯酸酯类，苯乙烯-丙烯腈-甲基丙烯酸甲酯共聚物、苯乙烯-丙烯腈共聚物、苯乙烯-甲基丙烯酸甲酯共聚物等。 核层为聚丙烯酸丁酯、苯乙烯-丁二烯共聚物、硅橡胶等。
一般的，三层核-壳结构增韧剂外层为聚丙烯酸酯类，苯乙烯-丙烯腈-甲基丙烯酸甲酯共聚物、苯乙烯-丙烯腈共聚物、苯乙烯-甲基丙烯酸甲酯共聚物等，中间橡胶层为聚丙烯酸丁酯、苯乙烯-丁二烯共聚物、硅橡胶等，里层为聚丙烯酸酯类，苯乙烯-丙烯腈-甲基丙烯酸甲酯共聚物、苯乙烯-丙烯腈共聚物、苯乙烯-甲基丙烯酸甲酯共聚物等。
优选的，所述的两层核-壳结构增韧剂中壳层占两层核-壳结构增韧剂总重量的45-70％。
优选的，所述的三层核-壳结构增韧剂中间橡胶层占三层核-壳结构增韧剂总重量的25-45％。
上述优选的层占比，是为了提升核-壳增韧剂在聚丙烯酸酯类聚合物基体中的相容性，减少增韧剂与树脂基体因为弯折后位移导致的微小空隙空洞话而产生折白。
为了得到增韧效率和透明度、抗折白性能之间的平衡，优选的，两层核-壳结构增韧剂占增韧剂总重量份的20-35％。
在对三层核-壳结构增韧剂和两层核-壳结构增韧剂的微观组成进行设计下，优选的，所述的增韧剂和聚丙烯酸酯类聚合物的折光率差值小于0.010。在聚丙烯酸酯类聚合物复合材料中，增韧剂是类似岛式的分布在树脂基体中，增韧剂和基体直接存在连接的过渡面，如果两种物质的折光率相差大，则透光率低，因此，增韧剂和树脂基体的折光率差值越小，透明度越高。当聚丙烯酸酯类聚合物为PMMA时折射率一般约为1.49，此时使用的增韧剂其折射率要接近该数值。两层核壳增韧剂主要是聚丙烯酸丁酯橡胶核层需要调整折射率与聚甲基丙烯酸甲酯壳层一致，即1.49。
所述的聚丙烯酸酯类聚合物选自聚丙烯酸甲酯类聚合物、聚丙烯酸乙酯类聚合物、聚丙烯酸丙酯类聚合物、聚丙烯酸丁酯类聚合物、聚丙烯酸戊酯类聚合物中的至少一种。
聚丙烯酸酯类聚合物主要是通过丙烯酸酯类化合物单体进行自由基聚合而得到。其中，可以是多种丙烯酸酯类化合物单体共聚。如聚甲基丙烯酸甲酯(PMMA)，其可以是甲基丙烯酸甲酯纯净物的自由基均聚，也可以是甲基丙烯 酸甲酯与其他丙烯酸酯类化合物的混合物自由基共聚。其他丙烯酸酯类化合物可以是丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丙酯、甲基丙烯酸正丁酯、甲基丙烯酸叔丁酯、甲基丙烯酸异丁酯、甲基丙烯酸戊酯、甲基丙烯酸2-乙基己酯等。
本发明可以添加抗紫外线剂等耐候剂，制备成高透明度、高柔韧性的抗紫外线薄膜，按重量份计，还包括0.3-10份的耐候剂；所述的耐候剂选自苯并三挫类紫外吸收剂、二苯甲酸类紫外吸收剂、HALS类化合物中的至少一种。所用的紫外吸收剂具有优异的热稳定性。
所述的苯并三挫类紫外吸收剂可选自2-(2’-羟基-5’-甲基)-苯并三唑、2-(3’,5’-二叔丁基-2’-羟基)-苯并三唑、2-(2’-羟基-3’-异丁基-5’-叔丁基)-苯并三唑、2-(2’-羟基-3’,5’-双(1,1-二甲基苯基)-苯并三唑、2-(2’-羟基-5’-叔辛基)-苯并三唑、2-(2’-羟基-3’-(1,1-二甲基苯基)-5’-[1,1,3,3-四甲基丁基]-苯并三唑、2,2’亚甲基-(6-(2H-苯并三唑)-4-叔辛基)苯酚中的至少一种。
所述的HALS化合物选自癸二酸双2,2,6,6-四甲基哌啶醇酯、N,N’-(2,2,6,6-四甲基,4-胺基哌啶)-间苯二酰胺，癸二酸双1-辛氧基-2,2,6,6-四甲基哌啶醇酯，甲基丙烯酸(1,2,2,6,6-五甲基哌啶醇)酯中的至少一种。
根据加工性能、阻燃性能、美观等，还可以包括0.2-5份的助剂，所述助剂选自热稳定剂、抗氧剂、抗滴落剂、润滑剂、增塑剂中的至少一种。
所述润滑剂为硬脂酸金属盐类润滑剂、硬脂酸烷基酯类润滑剂、硬脂酸季戊四醇酯类润滑剂、石蜡或褐煤蜡。
抗滴落剂选自聚四氟乙烯、硅酮包覆的聚四氟乙烯、甲基丙烯酸酯聚合物包覆的聚四氟乙烯中的至少一种。
所述热稳定剂为有机亚磷酸酯，优选为亚磷酸三苯酯、亚磷酸三-(2,6-二甲基苯基)酯、亚磷酸三-壬基苯基酯、二甲基苯膦酸酯或磷酸三甲酯。
所述抗氧剂为有机亚磷酸酯、烷基化的一元酚或者多元酚、多元酚和二烯的烷基化反应产物、对甲酚或者二环戊二烯的丁基化反应产物、烷基化的氢醌类、羟基化的硫代二苯基醚类、亚烷基-双酚、苄基化合物或多元醇酯类抗氧剂。
所述增塑剂为邻苯二甲酸酯。
聚丙烯酸酯类聚合物复合材料的制备方法，包括以下步骤：按照配比称量各组分，将聚丙烯酸酯类聚合物、增韧剂、耐候剂投入高速混料机中混合均匀，再 经过挤出机挤出造粒(螺杆转速为300-500rpm，挤出机各段螺杆温度从加料口到机头依次设为一区温度80-100℃、二区温度160-180℃、三区温度190-210℃、四区温度190-210℃、五区温度190-210℃、六区温度180-200℃、七区温度180-200℃、八区温度190-210℃、九区温度190-210℃、机头温度200-220℃)，得到聚丙烯酸酯类聚合物复合材料。
所述的增韧剂的粒径为50-250nm；
优选的，所述的增韧剂的粒径为130-170nm。用扫描电镜观察，增韧剂会小岛式分布在树脂基体中，增韧剂的粒径分布呈正态分布的，增韧剂粒径分布的峰值在上述粒径范围内，复合材料的透明度和抗折白性能令人满意，增韧效率也能保持较高的水平。
上述的聚丙烯酸酯类聚合物复合材料的应用，用于阻隔紫外线薄膜或涂层。本发明具有如下有益效果
本发明主要通过选取特定的两层核壳结构增韧剂与特定的三层核壳结构增韧剂的复配，进一步的，缩小增韧剂与树脂基体之间的折光率之差，并且通过调节两种增韧剂的用量比来得到优良的透明度以及制备成薄膜反复对折不会断裂也无折白痕迹的优点使聚丙烯酸酯类聚合物复合材料具有良好的透明度、抗折白效果，以及良好的增韧效果。可以制备为透光率高、韧性好、反复对折不会有折白的薄膜，应用范围广泛。
具体实施方式
本发明通过以下实施例来进一步说明本发明，但是本发明不受以下实施例限制。
本发明所用原料均来源于市售产品。
PMMA：重均分子量为130000g/mol，折光率为1.49；
两层核-壳结构增韧剂A：壳层为聚甲基丙烯酸甲酯，核层为交联的丙烯酸丁酯与苯乙烯共聚物，壳层占两层核-壳结构增韧剂总重量的61％，折光率1.495，粒径分布在50-200nm之间；
两层核-壳结构增韧剂B：壳层为聚甲基丙烯酸甲酯，核层为交联的丙烯酸丁酯与苯乙烯共聚物，壳层占两层核-壳结构增韧剂总重量的75％，折光率1.480，粒径分布在50-200nm之间；
两层核-壳结构增韧剂C：壳层为聚甲基丙烯酸甲酯，核层为苯乙烯-丁二烯共聚物，壳层占两层核-壳结构增韧剂总重量的61％，折光率1.931，粒径分布在50-200nm之间；
三层核-壳结构增韧剂A：外层为聚甲基丙烯酸甲酯，中间橡胶层为交联的丙烯酸丁酯与苯乙烯共聚物，里层为聚甲基丙烯酸甲酯，中间橡胶层占三层核-壳结构增韧剂总重量的41％，折光率1.488，粒径分布在50-200nm之间；
三层核-壳结构增韧剂B：外层为聚甲基丙烯酸甲酯，中间橡胶层为交联的丙烯酸丁酯与苯乙烯共聚物，里层为聚甲基丙烯酸甲酯，中间橡胶层占三层核-壳结构增韧剂总重量的20％，折光率1.479，粒径分布在50-200nm之间；
三层核-壳结构增韧剂C：外层为聚甲基丙烯酸甲酯，中间橡胶层为硅橡胶，里层为聚甲基丙烯酸甲酯，中间橡胶层占三层核-壳结构增韧剂总重量的41％，折光率1.508，粒径分布在50-200nm之间；
抗氧剂：四[β-(3，5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯和三[2.4-二叔丁基苯基]亚磷酸酯复配物；
润滑剂：乙撑双硬脂酰胺。
耐候剂：TINUVIN 770DF，HALS化合物，癸二酸双2,2,6,6-四甲基哌啶醇酯；
实施例和对比例聚丙烯酸酯类聚合物复合材料的制备方法：按照配比称量各组分，将聚丙烯酸酯类聚合物、增韧剂、耐候剂、抗氧剂、润滑剂投入高速混料机中混合均匀，再经过挤出机挤出造粒(螺杆转速为300-500rpm，挤出机各段螺杆温度从加料口到机头依次设为一区温度80-100℃、二区温度160-180℃、三区温度190-210℃、四区温度190-210℃、五区温度190-210℃、六区温度180-200℃、七区温度180-200℃、八区温度190-210℃、九区温度190-210℃、机头温度200-220℃)，得到聚丙烯酸酯类聚合物复合材料。
各项性能测试方法：
(1)透明度：制成60um厚的薄膜，用透过率测试仪器测试。
(2)悬臂梁缺口冲击强度：按照GB1843-1996《塑料悬臂梁冲击试验方法》标准测试，摆锤能量2.75J，常温测试。
(3)抗折白：制成60um厚的薄膜，对折薄膜对光观察发白情况。严重程 度划分等级为：无、轻微、明显、严重。
表1：实施例各组分配比(重量份)及各性能测试结果
Figure PCTCN2020098134-appb-000001
表2：对比例各组分配比(重量份)及各性能测试结果
Figure PCTCN2020098134-appb-000002
Figure PCTCN2020098134-appb-000003
从实施例1-4可以看出，在本发明增韧剂复配条件下，随着增韧剂用量的上升，力学性能上升，并且可以减缓透明性能、抗折白性能的下降。
从实施例2/5/6/7可以看出，相同增韧剂用量的情况下，双层、三层核-壳结构增韧剂的复配比很关键，在优选的复配比下，力学性能、透明度、抗折白的综合性能较好，更有利于推广应用。
从实施例2/8可以看出，次选的双层、三层核-壳结构增韧剂中的结构配比，能够严重影响透明度。
从对比例1可以看出，不是所有的双层、三层核-壳结构增韧剂的复配都能够得到优良的透明度、力学性能、抗折白性能。
从对比例2-4可以看出，仅添加两层核-壳结构增韧剂，或者两层核-壳结构增韧剂添加比例过大，都会导致透明度的下降，以及抗折白性能变差。特别的，从对比例4可以看出，当两层核-壳结构增韧剂添加比例太小，虽然透明度(实际上还低于实施例中增韧剂用量为30份的例子)和抗折白性能能够满足需求，但是力学性能很差。

Claims (10)

  1. 一种聚丙烯酸酯类聚合物复合材料，其特征在于，按重量份计，包括以下组分：
    聚丙烯酸酯类聚合物    100份；
    增韧剂                15-100份；
    所述的增韧剂选自两层核-壳结构增韧剂和三层核-壳结构增韧剂的复配，两层核-壳结构增韧剂占增韧剂总重量份的10-45％。
  2. 根据权利要求1所述的聚丙烯酸酯类聚合物复合材料，其特征在于，所述的两层核-壳结构增韧剂的壳层为聚甲基丙烯酸甲酯，核层为交联的丙烯酸丁酯与苯乙烯共聚物；所述的三层核-壳结构增韧剂的外层为聚甲基丙烯酸甲酯，中间橡胶层为交联的丙烯酸丁酯与苯乙烯共聚物，里层为聚甲基丙烯酸甲酯。
  3. 根据权利要求2所述的聚丙烯酸酯类聚合物复合材料，其特征在于，所述的两层核-壳结构增韧剂中壳层占两层核-壳结构增韧剂总重量的45-70％。
  4. 根据权利要求2所述的聚丙烯酸酯类聚合物复合材料，其特征在于，所述的三层核-壳结构增韧剂中间橡胶层占三层核-壳结构增韧剂总重量的25-45％。
  5. 根据权利要求1-4任一项所述的聚丙烯酸酯类聚合物复合材料，其特征在于，两层核-壳结构增韧剂占增韧剂总重量份的20-35％。
  6. 根据权利要求1所述的聚丙烯酸酯类聚合物复合材料，其特征在于，所述的聚丙烯酸酯类聚合物选自聚丙烯酸甲酯类聚合物、聚丙烯酸乙酯类聚合物、聚丙烯酸丙酯类聚合物、聚丙烯酸丁酯类聚合物、聚丙烯酸戊酯类聚合物中的至少一种。
  7. 根据权利要求1或3或4所述的聚丙烯酸酯类聚合物复合材料，其特征在于，所述的增韧剂和聚丙烯酸酯类聚合物的折光率差值小于0.010。
  8. 根据权利要求1所述的聚丙烯酸酯类聚合物复合材料，其特征在于，按重量份计，还包括0.3-10份的耐候剂；所述的耐候剂选自苯并三挫类紫外吸收剂、二苯甲酸类紫外吸收剂、HALS类化合物中的至少一种；还可以包括0.2-5份的助剂，所述助剂选自热稳定剂、抗氧剂、抗滴落剂、润滑剂、增塑剂中的至少一种。
  9. 权利要求8所述的聚丙烯酸酯类聚合物复合材料的制备方法，其特征在于，包括以下步骤：按照配比称量各组分，将聚丙烯酸酯类聚合物、增韧剂、耐候剂投入高速混料机中混合均匀，再经过挤出机挤出造粒(螺杆转速为300-500rpm， 挤出机各段螺杆温度从加料口到机头依次设为一区温度80-100℃、二区温度160-180℃、三区温度190-210℃、四区温度190-210℃、五区温度190-210℃、六区温度180-200℃、七区温度180-200℃、八区温度190-210℃、九区温度190-210℃、机头温度200-220℃)，得到聚丙烯酸酯类聚合物复合材料。
  10. 根据权利要求9所述的聚丙烯酸酯类聚合物复合材料的制备方法，其特征在于，所述的增韧剂的粒径为50-250nm；优选的，所述的增韧剂的粒径为130-170nm。
PCT/CN2020/098134 2019-07-12 2020-06-24 一种聚丙烯酸酯类聚合物复合材料及其制备方法 Ceased WO2021008321A1 (zh)

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