WO2014032231A1 - Pmma composite material, co-extrusion molded plastic product and plastic product - Google Patents

Pmma composite material, co-extrusion molded plastic product and plastic product Download PDF

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Publication number
WO2014032231A1
WO2014032231A1 PCT/CN2012/080685 CN2012080685W WO2014032231A1 WO 2014032231 A1 WO2014032231 A1 WO 2014032231A1 CN 2012080685 W CN2012080685 W CN 2012080685W WO 2014032231 A1 WO2014032231 A1 WO 2014032231A1
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Prior art keywords
pmma
coextruded
pmma composite
composite material
cbt
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PCT/CN2012/080685
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French (fr)
Chinese (zh)
Inventor
安小革
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深圳市毅彩鸿翔塑料有限公司
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Priority to PCT/CN2012/080685 priority Critical patent/WO2014032231A1/en
Publication of WO2014032231A1 publication Critical patent/WO2014032231A1/en

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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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
    • B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2033/00—Use of polymers of unsaturated acids or derivatives thereof as moulding material
    • B29K2033/04—Polymers of esters
    • B29K2033/12—Polymers of methacrylic acid esters, e.g. PMMA, i.e. polymethylmethacrylate

Definitions

  • the invention relates to the field of plastic materials, in particular to a PMMA Composite materials and coextruded plastic products, as well as plastic articles that require high transparency and high impact resistance.
  • PMMA Polymethyl methacrylate
  • 'plexiglass' Polymethyl methacrylate
  • PMMA Polymethyl methacrylate
  • It has extremely high transparency and belongs to general plastic display panels, plastic products, decorations and other products.
  • PMMA The main features of plastic products are the following: crystal clear, light and strong, excellent weather resistance, easy processing, good chemical resistance and electrical insulation. However, the impact resistance and surface hardness are slightly poor, and it is easy to wipe the flowers, so the packaging requirements are high.
  • PMMA In order to overcome the above performance of PMMA, it is modified to form PMMA.
  • Composite materials for example, adding appropriate additives, such as compatibilizers, toughening agents, sometimes in order to improve processing properties, also add appropriate amount of processing aids, talc, bentonite, ethylene bis-stearic acid amide and other additives .
  • processing aids such as compatibilizers, toughening agents, sometimes in order to improve processing properties, also add appropriate amount of processing aids, talc, bentonite, ethylene bis-stearic acid amide and other additives .
  • a PMMA composite is provided to maintain PMMA. Based on the original superior performance, it improves its impact resistance, improves fluidity and coextrusion performance.
  • a PMMA composite comprising the following components by mass percent: polymethyl methacrylate 50%-95%, toughening agent 4%-50%, polybutylene terephthalate 0.1-20%.
  • a coextruded plastic article comprising a first coextruded material and a second coextruded material, the second coextruded material being formed as a film on the surface of the first coextruded material, the second coextruded material Is the above PMMA Composite material.
  • the above PMMA composite material is polymerized Cyclobutylene terephthalate to enhance its fluidity, and the addition of a toughening agent can improve its impact resistance and toughness.
  • the addition of the two does not affect the original PMMA.
  • Excellent performance such as maintaining its superior transparency, weather resistance, good chemical resistance and electrical insulation, thus improving the physical properties of PMMA and further expanding PMMA The scope of use.
  • the modified PMMA composite material has the characteristics of easy coloring and excellent weather resistance.
  • PMMA Composite materials and other coextruded materials have excellent adhesion, are not easy to delaminate, and have good toughness.
  • PMMA polymethyl methacrylate
  • acrylic or plexiglass PMMA It has excellent optical properties and is a highly transparent thermoplastic with a light transmittance of over 93%.
  • PMMA The features also include crystal clear, light and strong, weather resistant, easy to process, good chemical resistance and electrical insulation.
  • the mass percentage of PMMA is preferably 60% - 90%, more preferably 70-85%. PMMA in this range enables PMMA composites to exhibit more pronounced, high brightness and high transparency.
  • the toughening agent is a core-shell polymer.
  • the core component of the core-shell polymer material is a polyacrylate and the shell component is methyl methacrylate- Butadiene-styrene-terpolymer Or polymethyl methacrylate.
  • the polyacrylate may be polymethyl acrylate, polyethyl acrylate, polypropyl acrylate or polybutyl acrylate, etc., preferably polybutyl acrylate.
  • the shell component is preferably methyl methacrylate - butadiene - Styrene-terpolymer, which has good compatibility and can significantly enhance the toughness and impact resistance of PMMA.
  • the core of the core-shell polymer is a solid core that enhances PMMA Hardness, improve its mechanical properties, and the shell component is rubber structure, so as to be compatible with PMMA, polybutylene terephthalate can enhance its fusion with PMMA.
  • the refractive index of the core-shell polymer is preferably Around 1.40-1.49, preferably 1.49.
  • the toughening agent has a mass percentage of 10% - 30%.
  • Methyl methacrylate is commonly used in existing composite plastics - Butadiene-styrene terpolymer (MBS), acrylonitrile-butadiene-styrene copolymer (ABS), styrene-butadiene thermoplastic elastomer (SBS)
  • MFS butadiene-styrene terpolymer
  • ABS acrylonitrile-butadiene-styrene copolymer
  • SBS thermoplastic elastomer
  • the toughening agent of the core-shell structure of the present embodiment has excellent toughness and high hardness compared with these conventional toughening agents, and the impact resistance of PMMA is further improved, and the optical properties are better.
  • CBT Polybutylene terephthalate
  • PBT-like structure PBT is abbreviated as polybutylene terephthalate
  • CBT is usually based on PBT, which is used to cleave PBT into short-chain oligomers in a solution, and is closed into a ring shape. After mixing and depolymerizing according to different PBT raw materials, different low molecular weight cyclic oligomers are obtained. That is, different types of CBT are obtained.
  • the preferred CBT of this embodiment has a melting point of 160 ° C and a density of 1.3 g/cm 3 .
  • the mass percentage of the CBT of the present embodiment is preferably from 1% to 15%, more preferably from 1% to 10%. due to CBT has a higher cost. In order to reduce costs, a lower content can be selected, for example, in the range of 1% - 15%, which can not only improve its flow performance but also save costs.
  • PMMA of an embodiment of the present invention Composite materials, by adding the above content of CBT, have the following advantages:
  • the toughening agent is a core-shell polymer, CBT It can promote the flow and compatibility between rubber and PMMA as a core-shell structure;
  • the PMMA composite material further comprises a mass percentage of 0.1-18%.
  • Lubricants can be used to replace part of the CBT, to assist the lubrication of CBT, to promote fluidity, thereby avoiding excessive use of CBT and reducing production costs.
  • Lubricant dosage and CBT The amount is complementary to each other and serves to supplement the amount of CBT.
  • the mass percentage of CBT is preferably 1% - 10%
  • the mass percentage of lubricant is preferably 1-18%. .
  • the lubricant may also include montan wax, bis stearamide, ethylene bis stearamide (abbreviated as EBS), stearic acid amide, ester lubricant, stearyl erucamide, polyethylene wax or stearic acid. Acid, etc., and preferably to PMMA Performance such as transparency does not affect the ingredients.
  • the PMMA composite material further comprises an anti-UV agent having a mass percentage of 0.1-2% and a mass percentage of 0.1-2% antioxidant. Due to PMMA There are many kinds of polymers in the composite material. The polymer is sensitive to light and heat, and autocatalytic degradation reaction (aging) occurs. Therefore, adding appropriate anti-UV agents and antioxidants, the two cooperate with each other and complement each other to improve their stability. Sex.
  • the anti-UV agent may be a benzophenone compound or a benzotriazole compound, a hindered amine light stabilizer, a cyanoacrylate, and the antioxidant may be three (2,4-di-tert-butyl) phenyl phosphite, benzoquinone or hindered phenols.
  • the modified PMMA composite material has the characteristics of being easier to color and having excellent weather resistance, for example, it is easier to color than PVC, It is a good choice for PVC coextrusion, especially for profiles with long-term surface exposure. Therefore, preferably, PMMA
  • PMMA The composite material is further added with a pigment, for example, a coloring agent such as an organic pigment or an inorganic pigment, and a pigment to form a color PMMA. When applied, it can be made into colored plastic products, as well as color PMMA The co-extruded film of the material to meet the actual environmental needs.
  • the composite material is usually produced in the form of a masterbatch for later processing to form a desired plastic article, and this embodiment is produced by a pelletizer. Therefore, embodiments of the present invention also provide a plastic article comprising the above PMMA Composite material.
  • the plastic product may also contain other material components, and then processed by injection molding or extrusion to form a plastic product of a desired shape structure.
  • the formulation content of PMMA, core-shell polymer, CBT, lubricant, etc. After mixing, they are added together to a granulator and granulated at a temperature of 160 to 220 ° C to obtain a granular PMMA composite.
  • granular PMMA composites are obtained by extrusion or injection molding to obtain plastic products, and some processing aids can be added during processing.
  • this composite plastic PMMA It is especially used for injection molding of complex process molds. Due to its high fluidity, it maintains the original transparency of PMMA and can be injection molded even in complex plastic products.
  • Plastic products made of composite materials including but not limited to plastic parts, household goods, household appliances, computers and accessories, audio products, furniture, toys, automotive interior parts, lampshades in household appliances , lamps, transportation interior parts, sun visors, cosmetic boxes, crafts, decorations, hairdressing supplies, etc.
  • This embodiment also provides a PMMA from the above a composite coextruded coextruded plastic article comprising a first coextruded material and a second coextruded material, the second coextruded material being formed as a film on the surface of the first coextruded material, the second coextrusion
  • the material is the above PMMA Composite material.
  • the first coextruded material is a polymer material or plastic, such as PVC, polychlorohexene (UPVC), etc.
  • the first coextruded material forms the body structure of the product
  • PMMA The composite film form is formed on the surface of the body structure.
  • the first co-extruded material is made of PVC as the door and window profiled profile, and the granulated PMMA.
  • the composite material is coextruded in the form of a film on the surface of the profile, typically one or more surfaces for decoration (e.g., a PMMA film surface that can be colored).
  • PMMA composite film and PVC The profiled material has excellent adhesion, is not easy to delaminate, has good toughness, high impact resistance and excellent fluidity.
  • the co-extruded layer can be uniform even in the thinnest process during the co-extrusion process, and some existing film materials are, for example, PET It is not easy to process, the co-extrusion is uneven, and the bonding force is poor.
  • PMMA 95%
  • the terpolymer is a shell)
  • 1% of CBT is mixed, and then stirred and mixed uniformly in a high-speed mixer, and then added together to a granulator to maintain the temperature at 180 ° C -200 ° C for granulation.
  • PMMA composite The prepared PMMA composite material and PVC are co-extruded in a screw extruder, and the processing temperature ranges from 160 to 220. Between °C, coextruded plastic products such as doors and windows are formed.
  • the following table is a sample composition and performance table of the above Examples 1-8.
  • PMMA of Examples 5-8 The overall performance of the composite material is good, and the transparency is also 90%, indicating that PMMA is still maintained.
  • the light transmittance is good, the fluidity is also good, the thickness is uniform when forming the film, the impact resistance is strong, and the mechanical property is good.
  • the toughening agent is used MBS, although suitably enhanced toughness, is weaker than core-shell polymer and has insufficient mechanical properties when used with MBS.
  • Replace CBT with PBT although CBT is PBT Depolymerized low molecular weight oligomers, but CBT can significantly improve the flowability of PMMA.
  • PBT also has a certain effect on transparency and low adhesion.
  • the PMMA composite material of the present embodiment is polymerized. Cyclobutylene terephthalate to enhance its fluidity, and the addition of a toughening agent can improve its impact resistance and toughness. The addition of the two does not affect the original PMMA. Excellent performance, such as maintaining its superior transparency, weather resistance, good chemical resistance and electrical insulation, thus improving the physical properties of PMMA and further expanding PMMA The scope of use. Further, the modified PMMA composite material has the characteristics of easy coloring and excellent weather resistance. Especially as a co-extruded material when co-extruded with other materials, PMMA Composite materials and other coextruded materials have excellent adhesion, are not easy to delaminate, and have good toughness.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)

Abstract

The present invention relates to the field of plastics technology, and provides a PMMA composite material comprising the following components by mass percentages: PMMA 50%-95%, a toughening agent 4%-50%, and a polycyclobutylene terephthalate 0.1-20%. The present invention also provides the co-extrusion molded plastic products from the above-mentioned PMMA composite material. The present invention provides the plastic products from the above-mentioned PMMA composite material as well. The addition of polycyclobutylene terephthalate into PMMA increases flowability, and the addition of the toughening agent therein enhances the impact resistance and toughness, both of which do not influence the original excellent properties of PMMA, thereby improving the physical properties of PMMA, further expanding the range of use, and producing co-extrusion molded products having a uniform thickness.

Description

PMMA复合材料、共挤成型塑料制品和塑料制品PMMA composites, coextruded plastics and plastics 技术领域Technical field
本发明涉及塑料材料领域，具体涉及一种 PMMA 复合材料和共挤成型塑料制品，以及要求具有高透明、高抗冲的塑料制品。  The invention relates to the field of plastic materials, in particular to a PMMA Composite materials and coextruded plastic products, as well as plastic articles that require high transparency and high impact resistance.
背景技术Background technique
聚甲基丙烯酸甲酯（简称 PMMA ），俗称'有机玻璃'。 PMMA 具有极高的透明性，属于通用塑料显示面板、塑料制品、装饰品等产品中。 PMMA 塑料制品特色主要有以下几点：晶莹透明、质轻而强韧、耐侯性极佳、容易加工、良好的耐化学药品性能及电气绝缘性等。但耐冲击性及表面硬度均稍差，容易擦花，故对包装要求较高。 Polymethyl methacrylate (PMMA for short), commonly known as 'plexiglass'. PMMA It has extremely high transparency and belongs to general plastic display panels, plastic products, decorations and other products. PMMA The main features of plastic products are the following: crystal clear, light and strong, excellent weather resistance, easy processing, good chemical resistance and electrical insulation. However, the impact resistance and surface hardness are slightly poor, and it is easy to wipe the flowers, so the packaging requirements are high.
为克服 PMMA 上述性能不足，通过对其进行改性形成 PMMA 复合材料，例如，添加适当的添加剂，例如相容剂、增韧剂，有时为了提高加工性能，还添加适量的加工助剂，滑石粉、膨润土、乙撑双硬脂酸酰胺等改性助剂。虽然这些助剂会对 PMMA 的一些性能有改善，但是同时也对其原有的优点，例如透明度、耐侯性等有一定程序的影响，甚至降低了这些优越性能，限制了 PMMA 的使用范围，因此也存在相对不足。另外，在某些 PMMA 共挤成型制品中， PMMA 与其他共挤材料的结合力不足，容易脱层，从而降低使用寿命。 In order to overcome the above performance of PMMA, it is modified to form PMMA. Composite materials, for example, adding appropriate additives, such as compatibilizers, toughening agents, sometimes in order to improve processing properties, also add appropriate amount of processing aids, talc, bentonite, ethylene bis-stearic acid amide and other additives . Although these additives will Some of PMMA's performance has improved, but it also has a certain program impact on its original advantages, such as transparency, weather resistance, etc., and even reduces these superior performance, limiting PMMA The scope of use, and therefore there are relative deficiencies. In addition, in some PMMA co-extruded products, PMMA has insufficient bonding strength with other co-extruded materials and is easy to delaminate, thus reducing service life.
技术问题technical problem
有鉴于此，提供一种 PMMA 复合材料，旨在保持 PMMA 原有优越性能的基础上，提高其抗冲击性，改善流动性和共挤性能。 In view of this, a PMMA composite is provided to maintain PMMA. Based on the original superior performance, it improves its impact resistance, improves fluidity and coextrusion performance.
以及，提供一种具有所述PMMA复合材料的共挤成型塑料制品以及具有上述复合材料的高透明、高抗冲的塑料制品。 And, a coextruded plastic article having the PMMA composite material and a highly transparent, high impact plastic article having the above composite material are provided.
技术解决方案Technical solution
一种 PMMA 复合材料，其包含按质量百分含量计的下列成分：聚甲基丙烯酸甲酯 50%-95% ，增韧剂 4%-50% ，聚对苯二甲酸环丁二醇酯 0.1-20% 。A PMMA composite comprising the following components by mass percent: polymethyl methacrylate 50%-95%, toughening agent 4%-50%, polybutylene terephthalate 0.1-20%.
一种共挤成型塑料制品，包括第一共挤材料和第二共挤材料，所述第二共挤材料以覆膜形式形成于所述第一共挤材料表面，所述第二共挤材料是上述 PMMA 复合材料。A coextruded plastic article comprising a first coextruded material and a second coextruded material, the second coextruded material being formed as a film on the surface of the first coextruded material, the second coextruded material Is the above PMMA Composite material.
以及，一种塑料制品，其包含上述PMMA复合材料。 And, a plastic article comprising the above PMMA composite.
有益效果Beneficial effect
上述 PMMA 复合材料采用聚 对苯二甲酸环丁二醇酯，以增强其流动性，而加入增韧剂可提高其抗冲击性、韧性， 两者的 加入不影响 PMMA 的原有 的优越性能，例如保持其优越的透明度、耐侯性、良好的耐化学药品性能及电气绝缘性等，从而完善了 PMMA 的物性，进一步扩大了 PMMA 的使用范围。进一步，改性后的 PMMA 复合材料具有易着色、耐候性优等特点。尤其是在与其他材料共挤成型时作为共挤材料， PMMA 复合材料与其他共挤材料粘贴性极佳，不易脱层，韧性佳，同时结合了 PMMA 复合材料的抗冲性，改良的流动性，使 PMMA 复合材料在共挤过程中其共挤层即使在最薄也能均匀一致。制成塑料制品时，可充分发挥其高透明、高抗冲的优异性能 。 The above PMMA composite material is polymerized Cyclobutylene terephthalate to enhance its fluidity, and the addition of a toughening agent can improve its impact resistance and toughness. The addition of the two does not affect the original PMMA. Excellent performance, such as maintaining its superior transparency, weather resistance, good chemical resistance and electrical insulation, thus improving the physical properties of PMMA and further expanding PMMA The scope of use. Further, the modified PMMA composite material has the characteristics of easy coloring and excellent weather resistance. Especially as a co-extruded material when co-extruded with other materials, PMMA Composite materials and other coextruded materials have excellent adhesion, are not easy to delaminate, and have good toughness. At the same time, they combine the impact resistance of PMMA composites and improve the fluidity, making PMMA The coextruded layer of the composite material is uniform even at the thinnest during the coextrusion process. When made into plastic products, it can fully exert its high transparency and high impact resistance.
本发明的实施方式Embodiments of the invention
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。 In order to make the objects, technical solutions and advantages of the present invention more comprehensible, the present invention will be further described in detail below with reference to the embodiments. It is understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
本发明实施例的第一种 PMMA 复合材料包含按质量百分含量计的下列成分： The first PMMA composite of the embodiment of the invention comprises the following ingredients in terms of mass percent:
聚甲基丙烯酸甲酯 50%-95% ， Polymethyl methacrylate 50%-95%,
增韧剂 4%-50% ， Toughener 4%-50%,
聚对苯二甲酸环丁二醇酯 0.1-20% 。 Polybutylene terephthalate 0.1-20%.
其中，聚甲基丙烯酸甲酯（ PMMA ），俗称压克力或有机玻璃， PMMA 具有极为优越的光学性能，是一种高度透明的热塑性塑料，透光率可达 93% 以上，如前所述， PMMA 的特点还包括晶莹透明、质轻而强韧、耐侯性极佳、容易加工、良好的耐化学药品性能及电气绝缘性等。在本实施例的复合材料中， PMMA 的质量百分含量优选为 60%-90% ，更优选为 70-85% 。在此范围的 PMMA 能使 PMMA 复合材料表现出更为显著、光亮度很高，透明度很高的效果。 Among them, polymethyl methacrylate (PMMA), commonly known as acrylic or plexiglass, PMMA It has excellent optical properties and is a highly transparent thermoplastic with a light transmittance of over 93%. As mentioned above, PMMA The features also include crystal clear, light and strong, weather resistant, easy to process, good chemical resistance and electrical insulation. In the composite material of the present embodiment, the mass percentage of PMMA is preferably 60% - 90%, more preferably 70-85%. PMMA in this range enables PMMA composites to exhibit more pronounced, high brightness and high transparency.
本实施例中，增韧剂为核壳聚合物。优选地，核壳聚合物材料的核组分为聚丙烯酸酯，壳组分为 甲基丙烯酸甲酯- 丁二烯 - 苯乙烯 -三元共聚物 或者聚甲基丙烯酸甲酯。聚丙烯酸酯可以是聚丙烯酸甲酯、聚丙烯酸乙酯、聚丙烯酸丙酯或聚丙烯酸丁酯等，优选为聚丙烯酸丁酯。壳组分优选为 甲基丙烯酸甲酯- 丁二烯 - 苯乙烯 -三元共聚物 ，其既具有较好的相容性，又能显著增强 PMMA 的韧性和抗冲击性。核壳聚合物的核为固体核，可增强 PMMA 硬度，提升其力学性能，而壳组分为橡胶结构，以便与 PMMA 相容，聚对苯二甲酸环丁二醇酯能增强其与 PMMA 相融合。核壳聚合物的折射率优选在 1.40-1.49 左右，优选为 1.49 。增韧剂的质量百分含量为 10% - 30% 。现有的复合塑料中通常采用甲基丙烯酸甲酯 - 丁二烯-苯乙烯三元共聚物（ MBS) 、丙烯腈 - 丁二烯 - 苯乙烯共聚物（ ABS) 、苯乙烯 - 丁二烯热塑性弹性体（ SBS) 等作为增韧剂，本实施例的核壳结构的增韧剂与这些传统增韧剂相比，具有韧性极佳，硬度高，更大提高 PMMA 的抗冲击性能，而且光学性能较好。 In this embodiment, the toughening agent is a core-shell polymer. Preferably, the core component of the core-shell polymer material is a polyacrylate and the shell component is methyl methacrylate- Butadiene-styrene-terpolymer Or polymethyl methacrylate. The polyacrylate may be polymethyl acrylate, polyethyl acrylate, polypropyl acrylate or polybutyl acrylate, etc., preferably polybutyl acrylate. The shell component is preferably methyl methacrylate - butadiene - Styrene-terpolymer, which has good compatibility and can significantly enhance the toughness and impact resistance of PMMA. The core of the core-shell polymer is a solid core that enhances PMMA Hardness, improve its mechanical properties, and the shell component is rubber structure, so as to be compatible with PMMA, polybutylene terephthalate can enhance its fusion with PMMA. The refractive index of the core-shell polymer is preferably Around 1.40-1.49, preferably 1.49. The toughening agent has a mass percentage of 10% - 30%. Methyl methacrylate is commonly used in existing composite plastics - Butadiene-styrene terpolymer (MBS), acrylonitrile-butadiene-styrene copolymer (ABS), styrene-butadiene thermoplastic elastomer (SBS) As a toughening agent, the toughening agent of the core-shell structure of the present embodiment has excellent toughness and high hardness compared with these conventional toughening agents, and the impact resistance of PMMA is further improved, and the optical properties are better.
聚对苯二甲酸环丁二醇酯（简称 CBT ），具有大环寡聚酯结构（类 PBT 结构， PBT 是聚对苯二甲酸丁二醇酯的简称），是一种低粘环状聚酯。 CBT 通常是以 PBT 为原料，用催化剂在溶液中将 PBT 裂解为短链的齐聚物，并闭合成环状，根据不同 PBT 原料进行混合后解聚，获得不同低分子量环状齐聚物，即获得不同类型的 CBT 。本实施例优选的 CBT 熔点为 160 摄氏度，密度为 1.3g/cm3 。Polybutylene terephthalate (CBT), which has a macrocyclic oligoester structure (PBT-like structure, PBT is abbreviated as polybutylene terephthalate), is a low-viscosity cyclic poly ester. CBT is usually based on PBT, which is used to cleave PBT into short-chain oligomers in a solution, and is closed into a ring shape. After mixing and depolymerizing according to different PBT raw materials, different low molecular weight cyclic oligomers are obtained. That is, different types of CBT are obtained. The preferred CBT of this embodiment has a melting point of 160 ° C and a density of 1.3 g/cm 3 .
本实施例的 CBT 的质量百分含量优选为 1% - 15% ，更优选为 1% - 10% 。由于 CBT 造价较高，为降低成本，可选择较低含量，例如在 1% - 15% 范围内，既能发挥其改善流动性能的作用，又能节省成本。本发明 实施例的 PMMA 复合材料，通过加入上述含量的 CBT ，主要有以下优点： The mass percentage of the CBT of the present embodiment is preferably from 1% to 15%, more preferably from 1% to 10%. due to CBT has a higher cost. In order to reduce costs, a lower content can be selected, for example, in the range of 1% - 15%, which can not only improve its flow performance but also save costs. PMMA of an embodiment of the present invention Composite materials, by adding the above content of CBT, have the following advantages:
1. 极大改善 PMMA 流动性，而且能保持 PMMA 原有的优越物性，尤其能保持其透明度； 1. Greatly improve PMMA fluidity, and maintain PMMA's original superior physical properties, especially to maintain its transparency;
2. 促进增韧剂与 PMMA 之间的流动、相容，在本实施例中，增韧剂为核壳结构聚合物， CBT 能促进作为核壳结构壳的橡胶与 PMMA 之间的流动、相容； 2. Promote the flow and compatibility between the toughening agent and PMMA. In this embodiment, the toughening agent is a core-shell polymer, CBT It can promote the flow and compatibility between rubber and PMMA as a core-shell structure;
3. 与常用的一些润滑剂如聚乙烯蜡相比较， CBT 使用量少即能改善流动性，还能保持 PMMA 的原有优点，而聚乙烯蜡等润滑剂需要过量使用，不仅影响 PMMA 的物性，在加工过程中还容易打滑，不利于加工成型； 3. Compared with some commonly used lubricants such as polyethylene wax, the use of CBT can improve the flow and maintain PMMA. The original advantages, while the lubricants such as polyethylene wax need to be used excessively, which not only affects the physical properties of PMMA, but also slips easily during processing, which is not conducive to processing;
4. 将 PMMA 复合材料与其他聚合物材料共挤成型时，不会分层，使用时也不易脱层，粘合力强，经久耐用，而其他助剂会分层，结合不牢靠，使用寿命短； 4. Put PMMA When the composite material is co-extruded with other polymer materials, it will not be layered, and it will not be easily delaminated when used. The adhesive strength is strong and durable, while other additives will be layered, the combination is not reliable, and the service life is short;
5. 易于加工，不论结构形状多复杂的注塑，都能成型到位。 5. Easy to process, regardless of the complex shape of the injection molding, can be molded into place.
在本实施例中， PMMA 复合材料还包括质量百分含量为 0.1-18% 的润滑剂，润滑剂可适当替换部分量的 CBT ，起到辅助 CBT 的润滑作用，促进流动性，从而避免使用过多 CBT ，降低生产成本。润滑剂用量与 CBT 用量相辅相成，起补充 CBT 量的作用，例如， CBT 的质量百分含量优选为 1% - 10% ，润滑剂 质量百分含量优选为 1-18% 。润滑剂可以是还包括蒙旦蜡，双硬脂酰胺，乙撑双硬脂酰胺（简称 EBS ），硬脂酸酰胺，酯类润滑剂，十八烷酰芥酸酰胺，聚乙烯蜡或硬脂酸等，且优选对 PMMA 性能如透明度不影响的成分。 In this embodiment, the PMMA composite material further comprises a mass percentage of 0.1-18%. Lubricants, lubricants can be used to replace part of the CBT, to assist the lubrication of CBT, to promote fluidity, thereby avoiding excessive use of CBT and reducing production costs. Lubricant dosage and CBT The amount is complementary to each other and serves to supplement the amount of CBT. For example, the mass percentage of CBT is preferably 1% - 10%, and the mass percentage of lubricant is preferably 1-18%. . The lubricant may also include montan wax, bis stearamide, ethylene bis stearamide (abbreviated as EBS), stearic acid amide, ester lubricant, stearyl erucamide, polyethylene wax or stearic acid. Acid, etc., and preferably to PMMA Performance such as transparency does not affect the ingredients.
在本实施例中， PMMA 复合材料还包括质量百分含量为 0.1-2% 的防紫外光剂和质量百分含量为 0.1-2% 的抗氧化剂。由于 PMMA 复合材料中具有多种聚合物，聚合物对光热较敏感，会发生自催化降解反应（老化），因此，添加适当防紫外光剂和抗氧化剂，两者相互配合、相辅相成，以提高其稳定性。防紫外光剂可以是二苯甲酮类化合物或苯并三唑类化合物，受阻胺光稳定剂，氰基丙烯酸酯类，抗氧化剂可以是三 (2,4- 二叔丁基 ) 亚磷酸苯酯、苯醌或受阻酚类等。 In this embodiment, the PMMA composite material further comprises an anti-UV agent having a mass percentage of 0.1-2% and a mass percentage of 0.1-2% antioxidant. Due to PMMA There are many kinds of polymers in the composite material. The polymer is sensitive to light and heat, and autocatalytic degradation reaction (aging) occurs. Therefore, adding appropriate anti-UV agents and antioxidants, the two cooperate with each other and complement each other to improve their stability. Sex. The anti-UV agent may be a benzophenone compound or a benzotriazole compound, a hindered amine light stabilizer, a cyanoacrylate, and the antioxidant may be three (2,4-di-tert-butyl) phenyl phosphite, benzoquinone or hindered phenols.
另外，改性后的 PMMA 复合材料具有比易于着色，耐候性优的特点，例如，比 PVC 容易着色，在 PVC 共挤中是很好的选择，特别适用于表面长期暴露在户外的异型材。因此，较佳地， PMMA 复合材料进一步添加有颜料，例如，包括有机颜料、无机颜料等染色剂、颜料，形成彩色 PMMA 。应用时，即可制成彩色塑料制品，以及彩色 PMMA 料的共挤覆膜，以适应实际环境需求。 In addition, the modified PMMA composite material has the characteristics of being easier to color and having excellent weather resistance, for example, it is easier to color than PVC, It is a good choice for PVC coextrusion, especially for profiles with long-term surface exposure. Therefore, preferably, PMMA The composite material is further added with a pigment, for example, a coloring agent such as an organic pigment or an inorganic pigment, and a pigment to form a color PMMA. When applied, it can be made into colored plastic products, as well as color PMMA The co-extruded film of the material to meet the actual environmental needs.
上述 PMMA 复合材料通常制作成母粒形式，以便后期加工成型出所需的塑料制品，本实施例采用造粒机制作。因此，本发明实施例还提供一种塑料制品，其包含上述 PMMA 复合材料。当然，该塑料制品也可含有其他材料成份，再通过注塑或挤压等加工成型，制成所需形状结构的塑料制品。 Above PMMA The composite material is usually produced in the form of a masterbatch for later processing to form a desired plastic article, and this embodiment is produced by a pelletizer. Therefore, embodiments of the present invention also provide a plastic article comprising the above PMMA Composite material. Of course, the plastic product may also contain other material components, and then processed by injection molding or extrusion to form a plastic product of a desired shape structure.
具体地，先将配方含量的的 PMMA 、核壳聚合物、 CBT 、润滑剂等组分 共混合后，再一起加入到造粒机中，保持温度在 160~220°C 下进行造粒，得到粒状 PMMA 复合材料。可选择性地加入防紫外光剂和抗氧化剂，然后将粒状 PMMA 复合材料通过挤出成型或注塑成型获得塑料制品，加工过程中可加入一些加工助剂。另外，此复合塑料 PMMA ，特别用于复杂工艺模具的注塑，由于它的流动性极高，又保持了 PMMA 原有的透明性，即使在复杂的塑料制品也可注塑成型。 Specifically, the formulation content of PMMA, core-shell polymer, CBT, lubricant, etc. After mixing, they are added together to a granulator and granulated at a temperature of 160 to 220 ° C to obtain a granular PMMA composite. Optional anti-UV and anti-oxidant, then granular PMMA composites are obtained by extrusion or injection molding to obtain plastic products, and some processing aids can be added during processing. In addition, this composite plastic PMMA It is especially used for injection molding of complex process molds. Due to its high fluidity, it maintains the original transparency of PMMA and can be injection molded even in complex plastic products.
上述 PMMA 复合材料制成的塑料制品，例如塑料成品及半成品，包括但不限于家用电器中的塑胶件、家庭用品、家电用品、电脑及其配件、音响制品、家私、玩具、汽车内饰件、灯罩、灯具、运输工具内饰件、遮阳板、化妆盒、工艺品、装饰品、美发用品等。 Above PMMA Plastic products made of composite materials, such as plastic finished products and semi-finished products, including but not limited to plastic parts, household goods, household appliances, computers and accessories, audio products, furniture, toys, automotive interior parts, lampshades in household appliances , lamps, transportation interior parts, sun visors, cosmetic boxes, crafts, decorations, hairdressing supplies, etc.
本实施例还提供一种由上述 PMMA 复合材料共挤成型的共挤塑料制品，包括第一共挤材料和第二共挤材料，第二共挤材料以覆膜形式形成于所述第一共挤材料表面，所述第二共挤材料是上述 PMMA 复合材料。第一共挤材料为聚合物材料或者说塑料，例如 PVC 、聚氯已烯（ UPVC ）等，第一共挤材料成型出制品的本体结构，而 PMMA 复合材料覆膜形式形成于本体结构的表面。以异型塑钢门窗为例，第一共挤材料以 PVC 为门窗异型型材，造粒的 PMMA 复合材料以覆膜形式共挤形成于型材表面，通常是用于装饰的一个或多个表面（例如，可形成彩色的 PMMA 薄膜表面）。其中， PMMA 复合材料薄膜与 PVC 异型材粘贴性极佳，不易脱层，韧性佳，抗冲性高，流动性极好，在共挤过程中其共挤层即使在最薄也能均匀一致，而现有的一些薄膜材料例如 PET 等不易加工，共挤不均匀，结合力差。 This embodiment also provides a PMMA from the above a composite coextruded coextruded plastic article comprising a first coextruded material and a second coextruded material, the second coextruded material being formed as a film on the surface of the first coextruded material, the second coextrusion The material is the above PMMA Composite material. The first coextruded material is a polymer material or plastic, such as PVC, polychlorohexene (UPVC), etc., the first coextruded material forms the body structure of the product, and PMMA The composite film form is formed on the surface of the body structure. Taking the special-shaped plastic steel doors and windows as an example, the first co-extruded material is made of PVC as the door and window profiled profile, and the granulated PMMA. The composite material is coextruded in the form of a film on the surface of the profile, typically one or more surfaces for decoration (e.g., a PMMA film surface that can be colored). Among them, PMMA composite film and PVC The profiled material has excellent adhesion, is not easy to delaminate, has good toughness, high impact resistance and excellent fluidity. The co-extruded layer can be uniform even in the thinnest process during the co-extrusion process, and some existing film materials are, for example, PET It is not easy to process, the co-extrusion is uneven, and the bonding force is poor.
以下通过多个实施例来举例说明发光玻璃元件的不同组成及其制备方法，以及其性能等方面。 The different compositions of the luminescent glass elements and their methods of preparation, as well as their properties, etc., are exemplified below by various embodiments.
实施例 1 Example 1
将 95% 的 PMMA 、 4% 的核壳聚合物（以 甲基丙烯酸甲酯- 丁二烯 - 苯乙烯 -三元共聚物 为壳）、 1% 的 CBT 共混合后，在高速搅拌机中搅拌混合均匀后，一起加入到造粒机中，保持温度在 180°C -200°C 下进行造粒，得到 PMMA 复合材料。将制得的 PMMA 复合材料与 PVC 在螺杆挤出机中共挤成型，加工温度范围在 160~220 ℃之间，形成共挤塑料制品，如门窗等。 95% PMMA, 4% core-shell polymer (with methyl methacrylate-butadiene-styrene) - The terpolymer is a shell), 1% of CBT is mixed, and then stirred and mixed uniformly in a high-speed mixer, and then added together to a granulator to maintain the temperature at 180 ° C -200 ° C for granulation. PMMA composite. The prepared PMMA composite material and PVC are co-extruded in a screw extruder, and the processing temperature ranges from 160 to 220. Between °C, coextruded plastic products such as doors and windows are formed.
实施例 2 Example 2
将 90% 的 PMMA 、 4% 的核壳聚合物（以 甲基丙烯酸甲酯- 丁二烯 - 苯乙烯 -三元共聚物 为壳）、 3% 的 CBT 、 3% 的 润滑剂（ 蒙旦蜡）共混合后，在高速搅拌机中搅拌混合均匀后，一起加入到造粒机中，保持温度在 160°C -220°C 下进行造粒，得到 PMMA 复合材料。将制得的 PMMA 复合材料与 PVC 在螺杆挤出机中共挤成型，加工温度范围在 160~220 ℃之间，形成共挤塑料制品。 90% PMMA, 4% core-shell polymer (with methyl methacrylate-butadiene-styrene) - The terpolymer is shell), 3% CBT, 3% lubricant (Mondan wax) are mixed together, stirred and mixed in a high-speed mixer, and then added to the granulator together, maintaining the temperature at 160 ° C Granulation was carried out at -220 ° C to obtain a PMMA composite. The prepared PMMA composite material and PVC are co-extruded in a screw extruder, and the processing temperature ranges from 160 to 220. Between °C, a coextruded plastic article is formed.
实施例 3 Example 3
将 85% 的 PMMA 、 5% 的核壳聚合物（以 甲基丙烯酸甲酯- 丁二烯 - 苯乙烯 -三元共聚物 为壳）、 3% 的 CBT 、 3% 的 润滑剂（ EBS ）、 2% 的防紫外光剂 （ 苯并三唑类化合物） 、 2% 的抗氧化剂 （ 苯醌）共混合后，在高速搅拌机中搅拌混合均匀后，一起加入到造粒机中，保持温度在 200°C -220°C 下进行造粒，得到 PMMA 复合材料。将制得的 PMMA 复合材料与 PVC 在螺杆挤出机中共挤成型，加工温度范围在 160~220 ℃之间，形成共挤塑料制品。 85% PMMA, 5% core-shell polymer (with methyl methacrylate-butadiene-styrene) - terpolymer is shell), 3% CBT, 3% lubricant (EBS), 2% UV inhibitor (benzotriazole), 2% antioxidant ( After the benzoquinone is mixed, it is stirred and mixed uniformly in a high-speed mixer, and then added to a granulator to carry out granulation at a temperature of 200 ° C - 220 ° C to obtain a PMMA composite. Will be made PMMA composites and PVC are co-extruded in a screw extruder with a processing temperature range of 160 to 220 °C to form coextruded plastic products.
实施例 4 Example 4
将 80% 的 PMMA 、 8% 的核壳聚合物（以 甲基丙烯酸甲酯- 丁二烯 - 苯乙烯 -三元共聚物 为壳）、 5% 的 CBT 、 5% 的 润滑剂（ 硬脂酸酰胺）、 1% 的防紫外光剂 （ 苯并三唑类化合物） 、 1% 的抗氧化剂 （ 苯醌）共混合后，在高速搅拌机中搅拌混合均匀后，一起加入到造粒机中，保持温度在 160°C -220°C 下进行造粒，得到 PMMA 复合材料。将制得的 PMMA 复合材料与 PVC 在螺杆挤出机中共挤成型，加工温度范围在 160~220 ℃之间，形成共挤塑料制品。 80% PMMA, 8% core-shell polymer (with methyl methacrylate-butadiene-styrene) - terpolymer is shell), 5% CBT, 5% lubricant (stearic acid amide), 1% UV inhibitor (benzotriazole), 1% antioxidant ( After the benzoquinone is mixed, it is stirred and mixed uniformly in a high-speed mixer, and then added to a granulator to carry out granulation while maintaining the temperature at 160 ° C - 220 ° C to obtain a PMMA composite. Will be made PMMA composites and PVC are co-extruded in a screw extruder with a processing temperature range of 160 to 220 °C to form coextruded plastic products.
实施例 5 Example 5
将 75% 的 PMMA 、 15% 的核壳聚合物（以 甲基丙烯酸甲酯- 丁二烯 - 苯乙烯 -三元共聚物 为壳）、 0.5% 的 CBT 、 8% 的 润滑剂（ 硬脂酸）、 0.5% 的防紫外光剂 （ 苯并三唑类化合物） 、 1% 的抗氧化剂 （ 苯醌）共混合后，在高速搅拌机中搅拌混合均匀后，一起加入到造粒机中，保持温度在 160°C -220°C 下进行造粒，得到 PMMA 复合材料。将制得的 PMMA 复合材料与 PVC 在螺杆挤出机中共挤成型，加工温度范围在 160~220 ℃之间，形成共挤塑料制品。 75% PMMA, 15% core-shell polymer (with methyl methacrylate-butadiene-styrene) - terpolymer is shell), 0.5% CBT, 8% lubricant (stearic acid), 0.5% UV inhibitor (benzotriazole), 1% antioxidant ( After the benzoquinone is mixed, it is stirred and mixed uniformly in a high-speed mixer, and then added to a granulator to carry out granulation while maintaining the temperature at 160 ° C - 220 ° C to obtain a PMMA composite. Will be made PMMA composites and PVC are co-extruded in a screw extruder with a processing temperature range of 160 to 220 °C to form coextruded plastic products.
实施例 6 Example 6
将 70% 的 PMMA 、 10% 的核壳聚合物（以 甲基丙烯酸甲酯- 丁二烯 - 苯乙烯 -三元共聚物 为壳）、 8% 的 CBT 、 10% 的 润滑剂（ 酯类润滑剂）、 1% 的防紫外光剂 （ 苯并三唑类化合物） 、 1% 的抗氧化剂 （ 受阻酚类）共混合后，在高速搅拌机中搅拌混合均匀后，一起加入到造粒机中，保持温度在 160°C -220°C 下进行造粒，得到 PMMA 复合材料。将制得的 PMMA 复合材料与 PVC 在螺杆挤出机中共挤成型，加工温度范围在 160~220 ℃之间，形成共挤塑料制品。 70% PMMA, 10% core-shell polymer (with methyl methacrylate-butadiene-styrene) - terpolymer is shell), 8% CBT, 10% lubricant (ester lubricant), 1% UV inhibitor (benzotriazole), 1% antioxidant ( After the hindered phenols are mixed, they are stirred and mixed uniformly in a high-speed mixer, and then added together to a granulator to carry out granulation at a temperature of 160 ° C - 220 ° C to obtain a PMMA composite. Will be made PMMA composites and PVC are co-extruded in a screw extruder with a processing temperature range of 160 to 220 °C to form coextruded plastic products.
实施例 7 Example 7
将 65% 的 PMMA 、 20% 的核壳聚合物（以 甲基丙烯酸甲酯- 丁二烯 - 苯乙烯 -三元共聚物 为壳）、 4% 的 CBT 、 10% 的 润滑剂（ 十八烷酰芥酸酰胺）、 0.5% 的防紫外光剂 （ 二苯甲酮类化合物） 、 0.5% 的抗氧化剂 （ 三 (2,4- 二叔丁基 ) 亚磷酸苯酯）共混合后，在高速搅拌机中搅拌混合均匀后，一起加入到造粒机中，保持温度在 160°C -220°C 下进行造粒，得到 PMMA 复合材料。将制得的 PMMA 复合材料与 PVC 在螺杆挤出机中共挤成型，加工温度范围在 160~220 ℃之间，形成共挤塑料制品。 65% PMMA, 20% core-shell polymer (with methyl methacrylate-butadiene-styrene) - terpolymer is shell), 4% CBT, 10% lubricant (octadecanoyl erucamide), 0.5% UV inhibitor (benzophenone), 0.5% The antioxidant (tris(2,4-di-tert-butyl) phenyl phosphite) is mixed together, stirred and mixed in a high-speed mixer, and then added to the granulator together, maintaining the temperature at 160 ° C -220 ° C The granulation was carried out to obtain a PMMA composite. The prepared PMMA composite material and PVC are co-extruded in a screw extruder, and the processing temperature ranges from 160 to 220. Between °C, a coextruded plastic article is formed.
实施例 8 Example 8
将 60% 的 PMMA 、 20% 的核壳聚合物（以 甲基丙烯酸甲酯- 丁二烯 - 苯乙烯 -三元共聚物 为壳）、 10% 的 CBT 、 8% 的 润滑剂（ 十八烷酰芥酸酰胺）、 1% 的防紫外光剂 （ 二苯甲酮类化合物） 、 1% 的抗氧化剂 （ 三 (2,4- 二叔丁基 ) 亚磷酸苯酯）共混合后，在高速搅拌机中搅拌混合均匀后，一起加入到造粒机中，保持温度在 160°C -220°C 下进行造粒，得到 PMMA 复合材料。将制得的 PMMA 复合材料与 PVC 在螺杆挤出机中共挤成型，加工温度范围在 160~220 ℃之间，形成共挤塑料制品。 60% PMMA, 20% core-shell polymer (with methyl methacrylate-butadiene-styrene) - terpolymer is shell), 10% CBT, 8% lubricant (octadecanoyl erucamide), 1% UV inhibitor (benzophenone), 1% antioxidant ( After mixing (triphenyl bis(2,4-di-tert-butyl) phosphite), stir and mix well in a high-speed mixer, add them to the granulator together, and keep the temperature at 160 °C -220 °C. Grain, get PMMA composite. The prepared PMMA composite material is co-extruded with PVC in a screw extruder, and the processing temperature ranges from 160 to 220 ° C to form a coextruded plastic product.
空白例 Blank example
将 80% 的 PMMA 、 15 % 的（ MBS 作为增韧剂）、 4% 的 润滑剂（ EBS ）、 0.5% 的防紫外光剂 （ 二苯甲酮类化合物） 、 0.5% 的抗氧化剂 （ 三 (2,4- 二叔丁基 ) 亚磷酸苯酯）共混合后，在高速搅拌机中搅拌混合均匀后，一起加入到造粒机中，保持温度在 160°C -220°C 下进行造粒，得到 PMMA 复合材料。将制得的 PMMA 复合材料与 PVC 在螺杆挤出机中共挤成型，加工温度范围在 160~220 ℃之间，形成共挤塑料制品。 80% PMMA, 15% (MBS as a toughener), 4% lubricant (EBS), 0.5% anti-UV agent (benzophenone compound), 0.5% antioxidant (tris(2,4-di-tert-butyl) After the phenyl phosphite is mixed, it is stirred and mixed uniformly in a high-speed mixer, and then added together to a granulator to carry out granulation at a temperature of 160 ° C - 220 ° C to obtain a PMMA composite. Will be made PMMA composites and PVC are co-extruded in a screw extruder with a processing temperature range of 160 to 220 °C to form coextruded plastic products.
对比例 Comparative example
将 80% 的 PMMA 、 9% 的（ MBS 作为增韧剂）、 5% 的 CBT 、 5% 的 润滑剂（ EBS ）、 0.5% 的防紫外光剂 （ 二苯甲酮类化合物） 、 0.5% 的抗氧化剂 （ 三 (2,4- 二叔丁基 ) 亚磷酸苯酯）共混合后，在高速搅拌机中搅拌混合均匀后，一起加入到造粒机中，保持温度在 160°C -220°C 下进行造粒，得到 PMMA 复合材料。将制得的 PMMA 复合材料与 PVC 在螺杆挤出机中共挤成型，加工温度范围在 160~220 ℃之间，形成共挤塑料制品。 80% PMMA, 9% (MBS as a toughener), 5% CBT, 5% Lubricant (EBS), 0.5% UV inhibitor (benzophenone), 0.5% antioxidant (tris(2,4-di-tert-butyl) After the phenyl phosphite is mixed, it is stirred and mixed uniformly in a high-speed mixer, and then added together to a granulator to carry out granulation at a temperature of 160 ° C - 220 ° C to obtain a PMMA composite. Will be made PMMA composites and PVC are co-extruded in a screw extruder with a processing temperature range of 160 to 220 °C to form coextruded plastic products.
下表是上述实施例 1-8 的样品组成和性能表。从表中可看出，实施例 5-8 的 PMMA 复合材料整体性能较好，透明度还具有 90% ，说明还保持着 PMMA 透光性好的优点，流动性也较好，成型薄膜时厚度均匀，抗冲击性强，力学性能较好。在空白例中，只用传统润滑剂容易打滑，而且成型薄膜时厚度不均匀。在对比例中，增韧剂采用 MBS ，虽然适当增强韧性，但是相比核壳结构聚合物较弱，而且用 MBS 时力学性能不足。 CBT 替换为 PBT ，虽然 CBT 为 PBT 解聚成的低分子量的齐聚物，但是 CBT 能明显改善 PMMA 的流动性， PBT 对透明度还具有一定影响，附着力小。 The following table is a sample composition and performance table of the above Examples 1-8. As can be seen from the table, PMMA of Examples 5-8 The overall performance of the composite material is good, and the transparency is also 90%, indicating that PMMA is still maintained. The light transmittance is good, the fluidity is also good, the thickness is uniform when forming the film, the impact resistance is strong, and the mechanical property is good. In the blank example, only the conventional lubricant is easy to slip, and the thickness of the film is not uniform. In the comparative example, the toughening agent is used MBS, although suitably enhanced toughness, is weaker than core-shell polymer and has insufficient mechanical properties when used with MBS. Replace CBT with PBT, although CBT is PBT Depolymerized low molecular weight oligomers, but CBT can significantly improve the flowability of PMMA. PBT also has a certain effect on transparency and low adhesion.
序号 Serial number PMMA PMMA 增韧剂 Toughener CBT CBT 润滑剂 Lubricant 防紫外光剂 Anti-UV agent 抗氧化剂 Antioxidants 透明度 transparency 流动性 fluidity 抗冲击性 Impact resistance
实施例 1 Example 1 95% 95% 4% 4% 1% 1% 0 0 0 0 0 0 94% 94% 好 it is good 强 Strong
实施例 2 Example 2 90% 90% 4% 4% 3% 3% 4% 4% 0 0 0 0 93% 93% 好 it is good 强 Strong
实施例 3 Example 3 85% 85% 5% 5% 3% 3% 3% 3% 2% 2% 2% 2% 92% 92% 好 it is good 强 Strong
实施例 4 Example 4 80% 80% 8% 8% 5% 5% 5% 5% 1% 1% 1% 1% 92% 92% 好 it is good 强 Strong
实施例 5 Example 5 75% 75% 15% 15% 0.5% 0.5% 8% 8% 0.5% 0.5% 1% 1% 92% 92% 很好 well 很 强 Very strong
实施例 6 Example 6 70% 70% 10% 10% 8% 8% 10% 10% 1% 1% 1% 1% 91% 91% 很好 well 很 强 Very strong
实施例 7 Example 7 65% 65% 20% 20% 4% 4% 10% 10% 0.5% 0.5% 0.5% 0.5% 91% 91% 很好 well 很 强 Very strong
实施例 8 Example 8 60% 60% 20% 20% 10% 10% 8% 8% 1% 1% 1% 1% 91% 91% 很好 well 很 强 Very strong
空白例 Blank example 80% 80% 4% 4% 0 0 15% 15% 0.5% 0.5% 0.5% 0.5% 91% 91% 打滑，厚度不均 Slip, uneven thickness 弱 weak
对比例 Comparative example 80% 80% 9% (MBS) 9% (MBS) 5% (PBT) 5% (PBT) 5% 5% 0.5% 0.5% 0.5% 0.5% 86% 86% 流动性不足，厚度不均 Insufficient fluidity and uneven thickness 较强，力学性能不足 Strong, insufficient mechanical properties
因此，如上所述， 本实施例的 PMMA 复合材料采用聚 对苯二甲酸环丁二醇酯，以增强其流动性，而加入增韧剂可提高其抗冲击性、韧性， 两者的 加入不影响 PMMA 的原有 的优越性能，例如保持其优越的透明度、耐侯性、良好的耐化学药品性能及电气绝缘性等，从而完善了 PMMA 的物性，进一步扩大了 PMMA 的使用范围。进一步，改性后的 PMMA 复合材料具有易着色、耐候性优等特点。尤其是在与其他材料共挤成型时作为共挤材料， PMMA 复合材料与其他共挤材料粘贴性极佳，不易脱层，韧性佳，同时结合了 PMMA 复合材料的抗冲性，改良的流动性，使 PMMA 复合材料在共挤过程中其共挤层即使在最薄也能均匀一致。制成塑料制品时，可充分发挥其高透明、高抗冲的优异性能。 Therefore, as described above, the PMMA composite material of the present embodiment is polymerized. Cyclobutylene terephthalate to enhance its fluidity, and the addition of a toughening agent can improve its impact resistance and toughness. The addition of the two does not affect the original PMMA. Excellent performance, such as maintaining its superior transparency, weather resistance, good chemical resistance and electrical insulation, thus improving the physical properties of PMMA and further expanding PMMA The scope of use. Further, the modified PMMA composite material has the characteristics of easy coloring and excellent weather resistance. Especially as a co-extruded material when co-extruded with other materials, PMMA Composite materials and other coextruded materials have excellent adhesion, are not easy to delaminate, and have good toughness. At the same time, they combine the impact resistance of PMMA composites and improve the fluidity, making PMMA The coextruded layer of the composite material is uniform even at the thinnest during the coextrusion process. When it is made into a plastic product, it can fully exert its high transparency and high impact resistance.
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。 The above is only the preferred embodiment of the present invention, and is not intended to limit the present invention. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the protection of the present invention. Within the scope.

Claims (10)

  1. 一种 PMMA 复合材料，其特征在于，包含如下质量百分含量的成分：A PMMA composite characterized by comprising the following mass percent components:
    聚甲基丙烯酸甲酯 50%-95% ，Polymethyl methacrylate 50%-95%,
    增韧剂 4%-50% ，Toughener 4%-50%,
    聚对苯二甲酸环丁二醇酯 0.1-20% 。Polybutylene terephthalate 0.1-20%.
  2. 如权利要求 1 所述的 PMMA 复合材料，其特征在于，还包括质量百分含量为 0.1-18% 的润滑剂。The PMMA composite material according to claim 1, further comprising a mass percentage of 0.1 to 18% Lubricant.
  3. 如权利要求 1 所述的 PMMA 复合材料，其特征在于，还包括质量百分含量为 0.1-2% 的防紫外光剂和质量百分含量为 0.1-2% 的抗氧化剂。The PMMA composite according to claim 1, further comprising an anti-UV agent having a mass percentage of 0.1 to 2% and a mass percentage of 0.1-2% antioxidant.
  4. 如权利要求 1 所述的 PMMA 复合材料，其特征在于，所述聚甲基丙烯酸甲酯的质量百分含量为 60% - 90% ，所述聚对苯二甲酸环丁二醇酯的质量百分含量为 1% - 15% 。The PMMA composite according to claim 1, wherein the polymethyl methacrylate has a mass percentage of 60% - 90% The polybutylene terephthalate has a mass percentage of 1% to 15%.
  5. 如权利要求 1 所述的 PMMA 复合材料，其特征在于，所述 PMMA 复合材料添加有颜料。The PMMA composite material according to claim 1, wherein the PMMA composite material is added with a pigment.
  6. 如权利要求 1 所述的 PMMA 复合材料，其特征在于，所述增韧剂为核壳聚合物。The PMMA composite of claim 1 wherein the toughening agent is a core-shell polymer.
  7. 如权利要求 6 所述的 PMMA 复合材料，其特征在于，所述核壳聚合物材料的核组分为聚丙烯酸酯，壳组分为 甲基丙烯酸甲酯- 丁二烯 - 苯乙烯 -三元共聚物 或者聚甲基丙烯酸甲酯。 The PMMA composite according to claim 6, wherein the core component of the core-shell polymer material is a polyacrylate and the shell component is methyl methacrylate- Butadiene-styrene-terpolymer or polymethyl methacrylate.
  8. 如权利要求 1 所述的 PMMA 复合材料，其特征在于，所述增韧剂的质量百分含量为 10% - 30% 。 The PMMA composite according to claim 1, wherein the toughening agent has a mass percentage of 10% to 30%.
  9. 一种共挤成型塑料制品，包括第一共挤材料和第二共挤材料，所述第二共挤材料以共挤覆膜形式共挤于所述第一共挤材料表面，其特征在于，所述第二共挤材料是权利要求 1-8 任意一项所述的 PMMA 复合材料。 A coextruded plastic article comprising a first coextruded material and a second coextruded material, the second coextruded material being coextruded on the surface of the first coextruded material in the form of a coextruded film, characterized in that The second coextruded material is a claim 1-8 The PMMA composite of any of the above.
  10. 一种塑料制品，其特征在于，所述塑料制品包含权利要求 1-8 任意一项所述的PMMA复合材料。 A plastic article, characterized in that the plastic article comprises the PMMA composite of any one of claims 1-8.
PCT/CN2012/080685 2012-08-29 2012-08-29 Pmma composite material, co-extrusion molded plastic product and plastic product WO2014032231A1 (en)

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* Cited by examiner, † Cited by third party
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CN2661416Y (en) * 2003-06-24 2004-12-08 殷根华 Colorful profiled bar
CN101906234A (en) * 2010-08-12 2010-12-08 东莞市信诺橡塑工业有限公司 Polymethyl methacrylate composition and preparation method thereof
CN102618009A (en) * 2012-04-13 2012-08-01 大河宝利材料科技(苏州)有限公司 Modified polycarbonate with high flowability and preparation method thereof
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