WO2024021765A1 - 一种自粘膜用复合材料及其制备方法 - Google Patents

一种自粘膜用复合材料及其制备方法 Download PDF

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WO2024021765A1
WO2024021765A1 PCT/CN2023/093446 CN2023093446W WO2024021765A1 WO 2024021765 A1 WO2024021765 A1 WO 2024021765A1 CN 2023093446 W CN2023093446 W CN 2023093446W WO 2024021765 A1 WO2024021765 A1 WO 2024021765A1
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parts
composite material
adhesive film
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French (fr)
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谭东晓
夏玉涛
李君�
车新宝
刘政江
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威海恒瑞新型包装材料有限公司
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/16—Ethene-propene or ethene-propene-diene copolymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2439/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Derivatives of such polymers
    • C08J2439/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
    • C08J2439/06—Homopolymers or copolymers of N-vinyl-pyrrolidones

Definitions

  • the invention relates to the field of medical device packaging materials, specifically a composite material for self-adhesive films and a preparation method thereof.
  • Self-adhesive film is a highly transparent and elastic soft film. It has high tensile strength, tear strength and good puncture resistance. It is made of linear low-density polyethylene (LLDPE) as the main raw material with a few auxiliary materials evenly mixed, melted and plasticized by the extrusion system, and then passed through the machine head and molding die using a single-layer, double-layer or multi-layer co-extrusion process. A new type of packaging material. Self-adhesive film is another type of product in protective film. It has the advantages of being more environmentally friendly, cleaner, more stable, easy to fit, and not easy to fall off. Self-adhesive means that the surface is self-adhesive, not glued, and there is no glue residue after being removed from the product surface.
  • Patent CN202122537046.5 discloses a self-adhesive film for sterilization packaging of medical devices.
  • the self-adhesive film can be heat-sealed with medical dialysis paper base paper or coated dialysis paper and used to prepare sterilization packaging bags for medical devices; its structure It is: the base film is a composite plastic film composed of polyethylene and other plastics, and is divided into two surfaces: the front side and the back side. The front side is the printable side; the back side is the outer surface of the PE layer of the base film and the outer surface of the PE layer. Above the surface is a heat seal layer. After the self-adhesive film is heat-sealed with medical dialysis paper base paper or coated dialysis paper, the heat-sealing peeling force is in the range of 1.3N/15mm-8.0N/15mm.
  • Heat sealing peel strength and peeling integrity are usually relative. If the heat sealing peeling strength is high, the peeling integrity will be low, and fiber debris is likely to be generated on the peeling surface.
  • the heat sealing layer of medical packaging materials not only requires high heat sealing peel strength to avoid package rupture during sterilization operations, but also requires high peeling integrity requirements to prevent fiber debris from being produced on the peeling surface during peeling.
  • the object of the present invention is to provide a composite material for self-adhesive films with higher peel strength and higher peel integrity and a preparation method thereof.
  • the technical solution of the present invention is: a composite material for self-adhesive films, including 5-15 parts by weight of polyvinylpyrrolidone-iodine-polymethacryloyloxypropyltrialkyloxysilane ternary composite, 45 -75 parts by weight of propylene-ethylene copolymer, 8-35 parts by weight of ethylene derivative-acrylic acid-maleic anhydride terpolymer, 1-4 parts by weight of polyethylene wax, 0.1-0.5 parts by weight of antioxidant and 0.2- 1.5 parts by weight of PPA additive.
  • the chemical formula of the polyvinylpyrrolidone-iodine-polymethacryloyloxypropyltrialkyloxysilane ternary complex is [(PVP)mI 2 -(PMMPSi)n] .
  • Polyvinylpyrrolidone referred to as PVP
  • PVP Polyvinylpyrrolidone
  • the number average molecular weight of PVP used in medicine is 10,000--40,000.
  • PVP is not only miscible with water, but also soluble in many organic solvents such as alcohols, carboxylic acids, amines, and halogenated hydrocarbons.
  • Polyvinylpyrrolidone-iodine is a loose complex combining elemental iodine and PVP. Among them, polyvinylpyrrolidone plays the role of carrier and dissolving agent.
  • the polyvinylpyrrolidone-iodine-polymethacryloyloxypropyltrialkyloxysilane ternary complex contains iodine, which exerts an antibacterial effect by continuously releasing free iodine, denaturing and killing proteins, and is harmful to bacteria, Spores, fungi and viruses all have strong killing and disinfecting abilities.
  • the free iodine combined with the hydrophilic PVP component can improve the composite material
  • the polarity improves the direct bonding force with the base paper and improves the peel strength of the self-adhesive film.
  • the combination of free iodine and the hydrophilic PVP component has the effect of inhibiting the adhesion of fiber debris, so that when the package is opened, the self-adhesive film can be cleanly separated from the surface of the original paper material, ensuring the integrity of the peeling surface and avoiding Produce fibrous debris.
  • Polyvinylpyrrolidone-iodine-polymethacryloyloxypropyltrialkyloxysilane ternary complex contains polymethacryloyloxypropyltrialkyloxysilane, and the siloxane group will It is chemically bonded with the hydroxyl groups on the base paper fibers to improve the peel strength of the self-adhesive film. It can also provide the polymer with good film-forming properties and durability, extending the service life of the self-adhesive film.
  • the composite material for the self-adhesive film of the present invention meets the requirements for self-adhesiveness and heat sealing with base paper, and has sufficient strength, tensile strength, puncture strength, tearing strength and peeling strength. It also has high peeling integrity and is especially suitable for the heat sealing layer of sealing packaging materials for medical products.
  • the molar ratio of m to n in [(PVP)m-I2-(PMMPSi)n] is 80-97:2.5-19.5.
  • a method for preparing composite materials for self-adhesive membranes including the following steps: Step 1): Prepare polyvinylpyrrolidone-iodine-polymethacryloyloxypropyltrialkyloxysilane ternary composite [(PVP) The preparation of acetone solution of m-I2-(PMMPSi)n] is as follows: Mix vinylpyrrolidone, methacryloyloxypropyltrialkyloxysilane and a free radical initiator to obtain a mixture. Add 5-25 parts by weight of the mixture to 100 parts by weight of acetone.
  • Propylene-ethylene copolymer regulates breathability
  • ethylene derivative-acrylic acid-maleic anhydride terpolymer regulates self-adhesiveness
  • vinyl wax and PAA additives regulate processability
  • antioxidants prevent material aging and degradation, extending the life of the self-adhesive film.
  • the molar ratio of the free radical initiator AIBME and m+n in step 1) is 0.5-3:100.
  • the added amount of free radical initiator AIBME ensures the stability of the self-adhesiveness of the obtained material and ensures that the self-adhesive film has high peel strength.
  • AIBME (Dimethyl 2,2'-azobis(2-methylpropionate), the Chinese name is azobisisobutyric acid methyl ester, the molecular formula is C 10 H 14 N 2 O 4 .
  • the relative molecular mass is 226.23.
  • Azobisisobutyrate Methyl nitrile is the most commonly used azo initiator. Its characteristic is that the decomposition reaction is relatively smooth, only one free radical is produced, and the decomposition products are non-toxic.
  • the amount of elemental iodine added in step 1) is 0.01%-3% of the dry weight of (PVP)mI 2 -(PMMPSi)n.
  • step 1) PVP)m-I2-(PMMPSi)n ternary complex is prepared, the substituent R in the monomer MMPSi used is methyl or ethyl; during polymerization, the added MMPSi monomer can be its trimethyl group One of oxysilane, triethoxysilane or a mixture of the two in any ratio.
  • the ethylene derivative structural unit is a polymerized unit of ethylene, propylene or 1-butene.
  • the composite material for the self-adhesive film of the present invention reduces the cost.
  • the I 2 in the [(PVP)mI 2 -(PMMPSi)n] ternary composite has high peel strength and self-cleaning ability, which can ensure the self-adhesive film. It can completely and cleanly detach from the interface during peeling, thereby ensuring that the peeling interface is clean and smooth without fiber debris. It is especially suitable for sealing packaging materials of medical products.
  • the self-adhesive film prepared by the composite material of the present invention has good adhesion effect on the surface of the adherend, strong adhesion, no residual glue, and is easy to peel off.
  • the surface layer and the self-adhesive layer are not easy to adhere when peeled off, and have good mechanical properties and stretchability. Strength and nominal strain rate at break are higher.
  • Example 1 Step 1) Mix vinylpyrrolidone (VP) with methacryloyloxypropyltrialkyloxysilane (MMPSi) and free radical initiator AIBME to obtain a mixture, vinylpyrrolidone and methacryloyloxy
  • the molar ratio of propyltrialkyloxysilane m:n is 90:15
  • the molar ratio of free radical initiator AIBME to m+n is 2:100
  • 25 parts by weight of the mixture is added to 100 parts by weight of acetone , under a nitrogen atmosphere, after 5 hours of polymerization at 90°C, add elemental iodine.
  • the amount of elemental iodine added is 3% of the dry weight of (PVP)mI 2 -(PMMPSi)n. Continue stirring at 50°C for 20 minutes to obtain (PVP)mI 2 -(PMMPSi)n acetone solution, yield 100%.
  • Step 2 Preparation of composite materials for self-adhesive membranes, the (PVP)mI 2 -(PMMPSi)n acetone solution prepared in the above step 1), wherein the dry matter weight of the (PVP)mI 2 -(PMMPSi)n ternary composite It is 5 parts by weight, 45 parts by weight of propylene-ethylene copolymer, 8 parts by weight of ethylene derivative-acrylic acid-maleic anhydride terpolymer, 1 part by weight of polyethylene wax, 0.1 part by weight of antioxidant and 0.2 part by weight of PPA Add the additive to the mixer, stir at a speed of 1000r/min, and evaporate to recover the solvent acetone to obtain a composite material that can be used for self-adhesive films.
  • the dry matter weight of the (PVP)mI 2 -(PMMPSi)n ternary composite It is 5 parts by weight, 45 parts by weight of propylene-ethylene copolymer, 8 parts by weight of ethylene derivative-acrylic
  • Example 2 Step 1) Mix vinylpyrrolidone (VP) with methacryloyloxypropyltrialkyloxysilane (MMPSi) and free radical initiator AIBME to obtain a mixture, vinylpyrrolidone and methacryloyloxy
  • VP vinylpyrrolidone
  • MMPSi methacryloyloxypropyltrialkyloxysilane
  • AIBME free radical initiator
  • the amount of elemental iodine added is 2% of the dry weight of (PVP)mI 2 -(PMMPSi)n. Continue stirring at 50°C for 60 minutes to obtain (PVP)mI 2 -(PMMPSi)n acetone solution, yield 100%.
  • Step 2 Preparation of composite materials for self-adhesive membranes, the (PVP)mI 2 -(PMMPSi)n acetone solution prepared in the above step 1), wherein the dry matter weight of the (PVP)mI 2 -(PMMPSi)n ternary composite It is 15 parts by weight, 75 parts by weight of propylene-ethylene copolymer, 35 parts by weight of ethylene derivative-acrylic acid-maleic anhydride terpolymer, 4 parts by weight of polyethylene wax, 0.5 parts by weight of antioxidant and 1.5 parts by weight of PPA Add the additive to the mixer, stir at a speed of 100r/min, and evaporate to recover the solvent acetone to obtain a composite material that can be used for self-adhesive films.
  • the dry matter weight of the (PVP)mI 2 -(PMMPSi)n ternary composite It is 15 parts by weight, 75 parts by weight of propylene-ethylene copolymer, 35 parts by weight of ethylene derivative-acrylic acid
  • Example 3 Step 1) Mix vinylpyrrolidone (VP) with methacryloyloxypropyltrialkyloxysilane (MMPSi) and free radical initiator AIBME to obtain a mixture, vinylpyrrolidone and methacryloyloxy
  • the molar ratio of propyltrialkyloxysilane m:n is 80:2.5
  • the molar ratio of free radical initiator AIBME to m+n is 0.5:100
  • the amount of elemental iodine added is 0.01% of the dry weight of (PVP)mI 2 -(PMMPSi)n. Continue stirring at 50°C for 40 minutes to obtain (PVP)mI 2 -(PMMPSi)n acetone solution, yield 100%.
  • Step 2 Preparation of composite materials for self-adhesive membranes, the (PVP)mI 2 -(PMMPSi)n acetone solution prepared in the above step 1), wherein the dry matter weight of the (PVP)mI 2 -(PMMPSi)n ternary composite It is 10 parts by weight, 60 parts by weight of propylene-ethylene copolymer, 20 parts by weight of ethylene derivative-acrylic acid-maleic anhydride terpolymer, 3 parts by weight of polyethylene wax, 0.3 parts by weight of antioxidant and 1 part by weight of PPA Add the additive to the mixer, stir at a speed of 500r/min, and evaporate to recover the solvent acetone to obtain a composite material that can be used for self-adhesive films.
  • the dry matter weight of the (PVP)mI 2 -(PMMPSi)n ternary composite It is 10 parts by weight, 60 parts by weight of propylene-ethylene copolymer, 20 parts by weight of ethylene derivative-acrylic acid
  • Experimental Example 4 Use the composite material for self-adhesive film prepared in Example 1 to prepare a self-adhesive film and the base paper to prepare a composite film.
  • Heat sealing temperature 200°C
  • heat sealing pressure 0.5Mpa
  • heat sealing time 2 seconds.
  • Example 5 The composite material for self-adhesive film prepared in Example 2 was used to prepare a self-adhesive film and the base paper to prepare a composite film.
  • the heat sealing time 2 seconds.
  • the right-angle tear force was measured according to the standard of "Plastic Tear Strength Test Method” QB/T1130-91, and the test results are shown in Table 2; the heat seal peeling force was measured according to the “Soft Composite Plastic Material Peeling Test Method” GB8808, and the test results are shown in the table 2; Measured according to "Plastic Film Pendulum Impact Test Method” GB8809, the test results are shown in Table 2.
  • the self-adhesive film prepared by the self-adhesive film composite material of the present invention has higher tensile strength and nominal strain rate at break, lower dynamic friction coefficient, and higher static friction coefficient. After compounding with the base paper, it has higher right-angle tearing force and heat sealing peeling force, and has good pendulum impact resistance. It has strong adhesion, good stability, no residual glue, and is easy to peel off. The surface layer and the self-adhesive layer are not easy to stick to each other when peeled off. It is easy to unroll and is convenient to use.

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Abstract

本发明提供一种自粘膜用复合材料及其制备方法，自粘膜用复合材料包括聚乙烯基吡咯烷酮-碘-聚甲基丙烯酰氧基丙基三烷基氧基硅烷三元复合物、丙烯-乙烯共聚物、乙烯衍生物-丙烯酸-马来酸酐三元共聚物，聚乙烯蜡、抗氧化剂和PPA助剂。本发明自粘膜用复合材料除了具有较高的剥离强度，还具有复合防污能力，在剥离时能够从界面自行脱落，从而保证剥离界面完整，避免纤维碎屑产生。该材料所制备的自粘膜具有较高的强度，包括拉伸强度、戳穿强度、撕裂强度以及剥离强度等。同时满足剥离完整性要求，尤其适合于医用制品的封口包装材料。

Description

一种自粘膜用复合材料及其制备方法 技术领域
本发明涉及医疗器械包装材料领域，具体的是一种自粘膜用复合材料及其制备方法。
 背景技术
自粘膜，是一种高透明而富有弹性的柔软薄膜。它具有较高的拉伸强度，撕裂强度以及良好的耐刺穿性。以线性低密度聚乙烯（LLDPE）为主要原料加入少许辅料均匀混合，经挤出系统熔融塑化然后再经机头以及成型模具采用单层、双层或多层共挤流涎工艺制成的一种新型包装材料。自粘膜是保护膜中另一类型的产品。具有更环保，更洁净，更稳定，贴合方便，不易脱落等优点。自粘意为表面自带粘性，而非涂胶，从产品表面撕除后无残胶。
与普通包装不同，许多医疗器械需要在使用前一直处于无菌条件下保存，避免因医用材料器械引起医疗感染事故，因此对医用包装袋阻菌性能要求及其严格。对于需要进行灭菌操作的医用包装袋，尤其是利用环氧乙烷的方式进行灭菌，包装袋需要具有一定的透气性来允许环氧乙烷进入包装袋内，对包装袋的内容物进行灭菌操作。本身并不具有透气性或透气性较差，因此使用自粘膜作为医用包装袋的原料需要结合其他具有透气性的材料，才能达到允许使用环氧乙烷进行灭菌消毒的要求。
专利CN202122537046.5公开了一种用于医疗器械灭菌包装的自粘膜，该自粘膜可以与医用透析纸原纸或涂层透析纸热封，用于制备医疗器械的灭菌包装袋；它的结构为：基膜为聚乙烯与其它塑料组成的复合塑料膜，分为正面和反面两个表面，所述正面是可印刷面；所述的反面是基膜的PE层外表面、PE层的外表面之上是热封层。该自粘膜与医用透析纸原纸或涂层透析纸热封后，热封剥离力在1.3N/15mm-8.0N/15mm的范围内。
热封剥离强度与剥离完整性通常是相对的，热封剥离强度高，剥离完整性就低，剥离面容易产生纤维碎屑。医用包装材料热封层不但需要较高的热封剥离强度，避免在灭菌操作时包装破裂，还需要较高的剥离完整性要求，以防止在剥离时，剥离面产生纤维碎屑。
 技术问题
本发明的目的是提供一种具有较高剥离强度和较高剥离完整性的自粘膜用复合材料及其制备方法。
 技术解决方案
本发明的技术方案是：一种自粘膜用复合材料，包括5-15重量份的聚乙烯基吡咯烷酮-碘-聚甲基丙烯酰氧基丙基三烷基氧基硅烷三元复合物、45-75重量份的丙烯-乙烯共聚物、8-35重量份的乙烯衍生物-丙烯酸-马来酸酐三元共聚物，1-4重量份聚乙烯蜡、0.1-0.5重量份抗氧化剂和0.2-1.5重量份PPA助剂，所述聚乙烯基吡咯烷酮-碘-聚甲基丙烯酰氧基丙基三烷基氧基硅烷三元复合物的化学式为[(PVP)m-I 2-(PMMPSi)n]。
聚乙烯基吡咯烷酮简称PVP，是一种无毒的水溶性高分子化合物，有很好的成膜性，用于医药的PVP数均分子量在10000--40000。PVP既能与水互溶，又能溶解于许多醇、羧酸、胺类、卤代烃等有机溶剂。聚乙烯基吡咯酮碘是元素碘和PVP相结合而成的疏松复合物。其中聚乙烯基吡咯烷酮起着载体和助溶作用。聚乙烯基吡咯烷酮-碘-聚甲基丙烯酰氧基丙基三烷基氧基硅烷三元复合物中含有碘，通过不断释放游离碘而发挥抗菌作用，使蛋白质变性、死亡，其对细菌、芽胞、真菌和病毒均有很强的杀灭能力和消毒作用。
聚乙烯基吡咯烷酮-碘-聚甲基丙烯酰氧基丙基三烷基氧基硅烷三元复合物除了碘元素具有杀菌效果外，游离的碘与亲水PVP组份相结合，能够提高复合材料的极性，提高与原纸直接的结合力，提高自粘膜的剥离强度。并且，游离的碘与亲水PVP组份相结合具有抑制纤维碎屑粘附的作用，使该复合物在包装打开时，使自粘膜从原纸材料表面清洁脱离，保证剥离面的完整性，避免产生纤维碎屑。
聚乙烯基吡咯烷酮-碘-聚甲基丙烯酰氧基丙基三烷基氧基硅烷三元复合物中含有聚甲基丙烯酰氧基丙基三烷基氧基硅烷，硅氧烷基团会与原纸纤维上的羟基化学键合，提高自粘膜的剥离强度，还能为聚合物提供良好的成膜性和耐久性，延长自粘膜的使用寿命。
本发明自粘膜用复合材料满足自粘及与原纸之间进行热合要求，具有足够的强度，拉伸强度、戳穿强度、撕裂强度以及剥离强度等。还具有较高的剥离完整性，尤其适合于医用制品的封口包装材料的热封层。
其中，[(PVP)m-I2-(PMMPSi)n]中m与n摩尔比为80-97:2.5-19.5。
经过多次实验，发明人发现聚乙烯基吡咯烷酮-碘-聚甲基丙烯酰氧基丙基三烷基氧基硅烷三元复合物中聚乙烯基吡咯烷酮与聚甲基丙烯酰氧基丙基三烷基氧基硅烷的摩尔比范围在80-97:2.5-19.5时，能够大大的延长自粘膜的老化时间，延长自粘膜的使用寿命30-50%。
一种自粘膜用复合材料的制备方法，包括如下步骤：步骤1）：制备聚乙烯基吡咯烷酮-碘-聚甲基丙烯酰氧基丙基三烷基氧基硅烷三元复合物[(PVP)m-I2-(PMMPSi)n]的丙酮溶液的制备，制备如下式（1）： 将乙烯基吡咯烷酮、甲基丙烯酰氧基丙基三烷基氧基硅烷和自由基引发剂混合获得混合物，将5-25重量份的混合物加入到100重量份的丙酮中，氮气氛下，在50-90℃条件下聚合反应5-15小时后，加入碘单质，在50℃继续搅拌20-60分钟，获得(PVP)m-I 2-(PMMPSi)n丙酮溶液，所述自由基引发剂为AIBME；步骤２）：自粘膜用复合材料的制备：将步骤１）中制备的(PVP)m-I 2-(PMMPSi)n丙酮溶液，其中含有(PVP)m-I 2-(PMMPSi)n干物质重量为5-15重量份、45-75重量份的丙烯-乙烯共聚物、8-35重量份的乙烯衍生物-丙烯酸-马来酸酐三元共聚物、1-4重量份聚乙烯蜡、0.1-0.5重量份抗氧化剂和0.2-1.5重量份PPA助剂混合，在100-1000r/min搅拌转速下加热蒸除丙酮，获得自粘膜用复合材料。
丙烯-乙烯共聚物调控透气性，乙烯衍生物-丙烯酸-马来酸酐三元共聚物调控自粘性，乙烯腊及PAA助剂调控加工性，抗氧化剂防止材料老化降解，延长自粘膜的寿命。
其中，步骤1）中自由基引发剂AIBME与m+n的摩尔比为0.5-3:100。
自由基引发剂AIBME的添加量确保所得材料的自粘的稳定，保证自粘膜具有较高的的剥离强度。
AIBME，（Dimethyl 2,2'-azobis(2-methylpropionate），中文名称为偶氮二异丁酸甲酯，分子式为C 10H 14N 2O 4。相对分子质量是226.23。偶氮二异丁腈酸甲酯是最常用的一种偶氮类引发剂。其特点是分解反应比较平稳，只产生1种自由基，分解产物无毒。
步骤1）中单质碘的添加量为(PVP)m-I 2-(PMMPSi)n干物质重量的0.01%-3%。
步骤1）中(PVP)m-I2-(PMMPSi)n三元复合物制备，所用单体MMPSi中的取代基R为甲基或乙基；聚合时，所添加的MMPSi单体可以是其三甲氧基硅烷、三乙氧基硅烷中的一种或二者任意比的混合物。
步骤2）中所使用的乙烯衍生物-丙烯酸-马来酸酐三元共聚物中乙烯衍生物结构单元为乙烯、丙烯或1-丁烯聚合单元。
 有益效果
本发明一种自粘膜用复合材料降低了成本，[(PVP)m-I 2-(PMMPSi)n]三元复合物中的I 2具有较高的剥离强度，还具有自洁能力，能够保证自粘膜在剥离时从界面完整的清洁脱离，从而保证剥离界面干净平整，无纤维碎屑，尤其适合于医用制品的封口包装材料。
本发明复合材料制备的自粘膜与被粘物表面贴附效果好、粘接力强、无残胶、易剥离，剥离时表层和自粘层不易粘连，且具有较好的力学性能，拉伸强度和断裂标称应变率较高。
 本发明的实施例
实施例1步骤1）将乙烯基吡咯烷酮（VP）与甲基丙烯酰氧基丙基三烷基氧基硅烷（MMPSi）和自由基引发剂AIBME混合获得混合物，乙烯基吡咯烷酮与甲基丙烯酰氧基丙基三烷基氧基硅烷摩尔比m:n为90:15，自由基引发剂AIBME与m+n的摩尔比为2:100，将25重量份的混合物加入到100重量份的丙酮中，氮气氛下，在90℃聚合反应5小时后，加入碘单质，单质碘的添加量为(PVP)m-I 2-(PMMPSi)n干物质重量的3%，在50℃继续搅拌20分钟，获得(PVP)m-I 2-(PMMPSi)n丙酮溶液，收率100%。
步骤2）自粘膜用复合材料的制备，将上述步骤1）所制得(PVP)m-I 2-(PMMPSi)n丙酮溶液，其中(PVP)m-I 2-(PMMPSi)n三元复合物干物质重量为5重量份、45重量份的丙烯-乙烯共聚物、8重量份的乙烯衍生物-丙烯酸-马来酸酐三元共聚物，1重量份聚乙烯蜡、0.1重量份抗氧化剂和0.2重量份PPA助剂加入到混合器，以1000r/min速度搅拌，并蒸除回收溶剂丙酮，获得可用于自粘膜用复合材料。
实施例2步骤1）将乙烯基吡咯烷酮（VP）与甲基丙烯酰氧基丙基三烷基氧基硅烷（MMPSi）和自由基引发剂AIBME混合获得混合物，乙烯基吡咯烷酮与甲基丙烯酰氧基丙基三烷基氧基硅烷摩尔比m:n为97:19.5，自由基引发剂AIBME与m+n的摩尔比为3:100，将5重量份的混合物加入到100重量份的丙酮中，氮气氛下，在50℃聚合反应15小时后，加入碘单质，单质碘的添加量为(PVP)m-I 2-(PMMPSi)n干物质重量的2%，在50℃继续搅拌60分钟，获得(PVP)m-I 2-(PMMPSi)n丙酮溶液，收率100%。
步骤2）自粘膜用复合材料的制备，将上述步骤1）所制得(PVP)m-I 2-(PMMPSi)n丙酮溶液，其中(PVP)m-I 2-(PMMPSi)n三元复合物干物质重量为15重量份、75重量份的丙烯-乙烯共聚物、35重量份的乙烯衍生物-丙烯酸-马来酸酐三元共聚物，4重量份聚乙烯蜡、0.5重量份抗氧化剂和1.5重量份PPA助剂加入到混合器，以100r/min速度搅拌，并蒸除回收溶剂丙酮，获得可用于自粘膜用复合材料。
实施例3步骤1）将乙烯基吡咯烷酮（VP）与甲基丙烯酰氧基丙基三烷基氧基硅烷（MMPSi）和自由基引发剂AIBME混合获得混合物，乙烯基吡咯烷酮与甲基丙烯酰氧基丙基三烷基氧基硅烷摩尔比m:n为80:2.5，自由基引发剂AIBME与m+n的摩尔比为0.5:100，将15重量份的混合物加入到100重量份的丙酮中，氮气氛下，在70℃聚合反应12小时后，加入碘单质，单质碘的添加量为(PVP)m-I 2-(PMMPSi)n干物质重量的0.01%，在50℃继续搅拌40分钟，获得(PVP)m-I 2-(PMMPSi)n丙酮溶液，收率100%。
步骤2）自粘膜用复合材料的制备，将上述步骤1）所制得(PVP)m-I 2-(PMMPSi)n丙酮溶液，其中(PVP)m-I 2-(PMMPSi)n三元复合物干物质重量为10重量份、60重量份的丙烯-乙烯共聚物、20重量份的乙烯衍生物-丙烯酸-马来酸酐三元共聚物，3重量份聚乙烯蜡、0.3重量份抗氧化剂和1重量份PPA助剂加入到混合器，以500r/min速度搅拌，并蒸除回收溶剂丙酮，获得可用于自粘膜用复合材料。
工业实用性
实验例1：采用实施例1所制备的自粘膜用复合材料制备自粘膜。
实验例2：采用实施例2所制备的自粘膜用复合材料制备自粘膜。
实验例3：采用实施例3所制备的自粘膜用复合材料制备自粘膜。
实验例4：采用实施例1所制备的自粘膜用复合材料制备自粘膜和原纸复合制备复合膜，热封温度：200℃、热封压力：0.5Mpa、热封时间：2秒。
实验例5：采用实施例2所制备的自粘膜用复合材料制备自粘膜和原纸复合制备复合膜，热封温度：200℃、热封压力：0.5Mpa、热封时间：2秒。
实验例6：采用实施例1所制备的自粘膜用复合材料制备自粘膜和原纸复合制备复合膜，热封温度：200℃、热封压力：0.5Mpa、热封时间：2秒。
拉伸强度、断裂标称应变率测试 按照《塑料拉伸性能的测定第3部分：薄塑和薄片的试验条件》GB/T1040.3-2016标 准测量拉伸强度和断裂伸长率，结果见表1；按照《塑料薄膜和薄片摩擦系数测定方法》GB10006-88标准测量摩擦系数；结果见表1。 按《塑料撕裂强度测试方法》QB/T1130-91的标准测量直角撕裂力，测试结果见表2；按《软质复合塑料材料剥离试验方法》GB8808测量热封剥离力，测试结果见表2；按《塑料薄膜抗摆摆锤冲击试验方法》GB8809 测量，测试结果见表2。
实验结果由实验例可以看出，本发明自粘膜复合材料所制备的自粘膜拉伸强度和断裂标称应变率较高，动摩擦系数较低，静摩擦系数较高。与原纸复合后直角撕裂力和热封剥离力较高，抗摆锤冲击性能好。粘着力强、稳定性好，无残胶、易剥离，剥离时表层和自粘层不易粘连，易解卷，方便使用。

Claims (5)

  1. 一种自粘膜用复合材料，其特征在于：包括5-15重量份的聚乙烯基吡咯烷酮-碘-聚甲基丙烯酰氧基丙基三烷基氧基硅烷三元复合物、45-75重量份的丙烯-乙烯共聚物、8-35重量份的乙烯衍生物-丙烯酸-马来酸酐三元共聚物，1-4重量份聚乙烯蜡、0.1-0.5重量份抗氧化剂和0.2-1.5重量份PPA助剂，所述聚乙烯基吡咯烷酮-碘-聚甲基丙烯酰氧基丙基三烷基氧基硅烷三元复合物的化学式为[(PVP) m-I 2-(PMMPSi) n]，其中m与n摩尔比为80-97:2.5-19.5，所述自粘膜用复合材料采用如下方法制备而成，包括如下步骤：步骤1）：制备聚乙烯基吡咯烷酮-碘-聚甲基丙烯酰氧基丙基三烷基氧基硅烷三元复合物[(PVP)m-I 2-(PMMPSi)n]，制备如下式（1）： 将乙烯基吡咯烷酮、甲基丙烯酰氧基丙基三烷基氧基硅烷和自由基引发剂混合获得混合物，将5-25重量份的混合物加入100重量份的丙酮中，氮气氛下，在50-90℃条件下聚合反应5-15小时后，加入碘单质，在50℃继续搅拌20-60分钟，获得(PVP)m-I 2-(PMMPSi)n丙酮溶液，所述自由基引发剂为AIBME；步骤２）：自粘膜用复合材料的制备：将步骤1）中制得的(PVP)m-I 2-(PMMPSi)n丙酮溶液，其中含有(PVP)m-I 2-(PMMPSi)n干物质重量为5-15重量份，45-75重量份的丙烯-乙烯共聚物、8-35重量份的乙烯衍生物-丙烯酸-马来酸酐三元共聚物、1-4重量份聚乙烯蜡、0.1-0.5重量份抗氧化剂和0.2-1.5重量份PPA助剂混合，在100-1000r/min搅拌转速下加热蒸除丙酮，获得自粘膜用复合材料。
  2. 根据权利要求1所述的自粘膜用复合材料，其特征在于：步骤1）中自由基引发剂AIBME与m+n的摩尔比为0.5-3:100。
  3. 根据权利要求2所述的自粘膜用复合材料，其特征在于：步骤1）中单质碘的添加量为(PVP) m-I 2-(PMMPSi) n干物质质量的0.01%-3%。
  4. 根据权利要求3所述的自粘膜用复合材料，其特征在于：步骤1）中(PVP) m-I 2-(PMMPSi) n三元复合物制备，所用单体MMPSi中的取代基R为甲基或乙基；聚合时，所添加的MMPSi单体可以是其三甲氧基硅烷、三乙氧基硅烷中的一种或二者任意比的混合物。
  5. 根据权利要求4所述的自粘膜用复合材料，其特征在于：步骤2）中所使用的乙烯衍生物-丙烯酸-马来酸酐三元共聚物中乙烯衍生物结构单元为乙烯、丙烯或1-丁烯聚合单元。
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