WO2019061757A1 - 一种耐老化木塑包装材料及其制备方法 - Google Patents

一种耐老化木塑包装材料及其制备方法 Download PDF

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WO2019061757A1
WO2019061757A1 PCT/CN2017/112136 CN2017112136W WO2019061757A1 WO 2019061757 A1 WO2019061757 A1 WO 2019061757A1 CN 2017112136 W CN2017112136 W CN 2017112136W WO 2019061757 A1 WO2019061757 A1 WO 2019061757A1
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parts
packaging material
plastic packaging
temperature
wood
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王静
王海峰
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苏州市一木包装材料有限公司
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
    • C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F289/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds not provided for in groups C08F251/00 - C08F287/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
    • C08H8/00—Macromolecular compounds derived from lignocellulosic materials
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C08K2003/3045—Sulfates

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  • the invention belongs to the field of wood plastic packaging materials, in particular to an aging resistant wood plastic packaging material and a preparation method thereof.
  • Wood-plastic composite is a composite material mainly made of wood or cellulose-based materials and plastics, which is a certain proportion of wood fiber (such as wood powder, straw powder, cotton straw powder, bamboo powder, A new type of material that has been pretreated to combine with a thermoplastic polymer resin or other material.
  • the new material is environmentally friendly and has good mechanical stability. It can exert the advantages of various components in the material and overcome the limitations of use due to low wood strength, high variability and low elastic modulus of organic materials. It has received more and more attention from people.
  • the existing polymer composite wood-plastic materials in the production process only pay attention to the mixing or reuse of several materials, as well as the improvement of basic mechanical properties, do not fully consider the compatibility of various materials and interface bonding, interface bonding ability and The diffusion and penetration of various materials at the interface cannot guarantee that the plant fibers can be fully dispersed in the polymer resin, and the wood/plastic interface has poor interaction.
  • the affinity between the two is low, and the bonding strength is low, thus causing the polymer composite wood-plastic material.
  • the mechanical properties and other performances are low; and the aging resistance is weak and cannot be applied continuously.
  • the object of the present invention is to provide an aging resistant wood plastic packaging material and a preparation method thereof, which are improved by aging wood powder and polypropylene plastic respectively to improve the aging resistance of wood plastic packaging materials.
  • Performance the interaction force at the wood/plastic interface is improved by adding various substances such as azodicarbonamide, so that the compatibility is good.
  • a method for preparing an aging resistant wood plastic packaging material comprises the following steps:
  • the film is formed by a film at a temperature of 190-210 ° C and a pressure of 8-12 MPa; the aging-resistant wood-plastic packaging material can be obtained after cooling.
  • the lignocellulosic fiber is 65 parts, the dimethyl sulfate is 8 parts, and the polyethylene glycol is 28 parts, and the reaction is carried out for 35 minutes under a pressure of 6.5 MPa.
  • step (2) 27 parts of the polypropylene particles, 6 parts of basic magnesium sulfate whiskers, 4 parts of cyclophosphamide, and 3 parts of p-hydroxypropiophenone were mixed and stirred for 7 minutes.
  • the extruder has an extrusion temperature of 160-180 ° C and a screw rotation speed of 20-30 rpm in the step (2).
  • step (3) 3 parts of azodicarbonamide, 2 parts of dicumyl peroxide, 7 parts of 4-butanediol ester and 16 parts of acrylic acid; and the reaction was stirred at a temperature of 108 ° C for 35 minutes.
  • step (4) the temperature is 185 ° C and the screw rotation speed is 35 rpm.
  • the temperature in the step (5) is 200 ° C and the pressure is 10 MPa.
  • the aging resistant wood plastic packaging material prepared as described in any of the above.
  • the invention has the following beneficial effects:
  • the invention relates to a method for preparing an aging resistant wood plastic packaging material, which comprises modifying the surface of the wood fiber by using dimethyl sulfate and polyethylene glycol, and passing through basic magnesium sulfate whisker, cyclophosphamide, p-hydroxypropiophenone
  • the polypropylene particles are modified to first improve the aging resistance of the wood fibers and the polypropylene particles. Subsequently, under the action of azodicarbonamide, dicumyl peroxide, 4-butanediol ester and acrylic acid, the interaction between the wood/plastic interface is enhanced, the interfacial bonding ability and the diffusion and penetration of various materials at the interface are increased.
  • the affinity between the two is improved, the bonding strength is high, the compatibility is good, and the overall performance is improved.
  • the film is formed by a film at a temperature of 210 ° C and a pressure of 8 MPa; the aging-resistant wood-plastic packaging material can be obtained after cooling.
  • the film is formed by a film at a temperature of 190 ° C and a pressure of 12 MPa; the aging-resistant wood-plastic packaging material can be obtained after cooling.
  • the film is formed by a film at a temperature of 200 ° C and a pressure of 10 MPa; the aging-resistant wood-plastic packaging material can be obtained after cooling.
  • the film is formed by a film at a temperature of 205 ° C and a pressure of 12 MPa; the aging-resistant wood-plastic packaging material can be obtained after cooling.
  • the film is formed by a film at a temperature of 200 ° C and a pressure of 10 MPa; the aging-resistant wood-plastic packaging material can be obtained after cooling.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Biochemistry (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Dry Formation Of Fiberboard And The Like (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Laminated Bodies (AREA)

Abstract

本发明公开了一种耐老化木塑包装材料的制备方法，将木质纤维粉碎至粒度为80-120目的木粉，加入硫酸二甲酯和聚乙二醇，置于高压反应容器中，在4-8MPa压力下，反应30-40min，得到改性木粉；将聚丙烯粒子、碱式硫酸镁晶须、环磷酰胺和对羟基苯丙酮混合搅拌5-10min；随后经挤出机熔融共混并造粒，得到改性聚丙烯粒子；将改性木粉和改性聚丙烯粒子混合，并加入偶氮二甲酰胺、过氧化二异丙苯、4-丁二醇酯和丙烯酸，在温度90-120℃搅拌反应20-40min；将混合物加入挤出机中，在温度175-190℃、螺杆转速25-45rpm下挤出；随后经模具在温度190-210℃、压力8-12MPa下压膜成型；待冷却后即可得到所述耐老化木塑包装材料。

Description

一种耐老化木塑包装材料及其制备方法 技术领域
本发明属于木塑包装材料领域，特别涉及一种耐老化木塑包装材料及其制备方法。
背景技术
伴随人们城镇化进程的加快，木材、化石能源等资源极大消耗，各类自然资源已将日趋枯竭，与此同时，人们环保意识逐步增强，木材材料也逐渐兴起。木塑复合材料(WPC)，是一种主要由木材或者纤维素为基础材料与塑料制成的复合材料，就是将一定比例的木纤维(如木粉、秸秆粉、棉杆粉、竹粉、果壳粉等)经过预处理使之与热塑性聚合物树脂或其他材料结合而成的一种新型材料。该新型材料既绿色环保又具有良好的力学稳定性，能发挥材料中各组分的优点，克服因木材强度低、变异性大及有机材料弹性模量低等造成的使用局限性，因此，愈来愈受到人们的广泛关注。
然而现有的高分子复合木塑材料生产过程中只注重几种物料的混合或再利用，以及基本力学性质的改进，未充分考虑各种材料的相容性和界面结合情况、界面结合能力及各种材料在界面的扩散、渗透等，不能保证植物纤维在高分子树脂中能充分分散，木/塑界面相互作用差，两者的亲和力低，结合强度低，因此造成高分子复合木塑材料的力学性能和其它使用性能较低；且耐老化性能较弱，无法持续应用。
发明内容
针对上述缺陷，本发明的目的是提供一种耐老化木塑包装材料及其制备方法，通过对木粉和聚丙烯塑料分别改性，提高木塑包装材料的耐老化 性能；通过加入偶氮二甲酰胺等多种物质提高木/塑界面的相互作用力，使其相容性良好。
一种耐老化木塑包装材料的制备方法，包含如下步骤：
(1)将60-70份木质纤维粉碎至粒度为80-120目的木粉，加入6-10份硫酸二甲酯和20-30份聚乙二醇，置于高压反应容器中，在4-8MPa压力下，反应30-40min，得到改性木粉；
(2)将20-30份聚丙烯粒子、5-8份碱式硫酸镁晶须、3-5份环磷酰胺和1-4份对羟基苯丙酮混合搅拌5-10min；随后经挤出机熔融共混并造粒，得到改性聚丙烯粒子；
(3)将步骤(1)所述改性木粉和步骤(2)所述改性聚丙烯粒子混合，并加入2-4份偶氮二甲酰胺、1-3份过氧化二异丙苯、4-9份4-丁二醇酯和15-20份丙烯酸，在温度90-120℃搅拌反应20-40min；
(4)将步骤(3)所得混合物加入挤出机中，在温度175-190℃、螺杆转速25-45rpm下挤出；
(5)随后经模具在温度190-210℃、压力8-12MPa下压膜成型；待冷却后即可得到所述耐老化木塑包装材料。
进一步的，步骤(1)中所述木质纤维为65份、硫酸二甲酯为8份、聚乙二醇28份，在6.5MPa压力下，反应35min。
进一步的，步骤(2)中所述聚丙烯粒子27份、碱式硫酸镁晶须6份、环磷酰胺4份和对羟基苯丙酮3份混合搅拌7min。
进一步的，步骤(2)中所述挤出机的挤出温度为160-180℃，螺杆转速20-30rpm。
进一步的，步骤(3)中所述偶氮二甲酰胺3份、过氧化二异丙苯2份、4-丁二醇酯7份和丙烯酸16份；在温度108℃搅拌反应35min。
进一步的，步骤(4)中温度185℃、螺杆转速35rpm。
进一步的，步骤(5)中所述温度200℃、压力10MPa。
上述任意一条所述制备得到的耐老化木塑包装材料。
本发明与现有技术相比，其有益效果为：
本发明所述一种耐老化木塑包装材料的制备方法，通过硫酸二甲酯和聚乙二醇对木质纤维表面进行改性，通过碱式硫酸镁晶须、环磷酰胺、对羟基苯丙酮对聚丙烯粒子进行改性，先提高木质纤维和聚丙烯粒子各自的耐老化性能。随后在偶氮二甲酰胺、过氧化二异丙苯、4-丁二醇酯和丙烯酸的作用下，木/塑界面相互作用增强，界面结合能力及各种材料在界面的扩散、渗透增加，两者亲和力提高，结合强度高，相容性好，整体性能得到提高。
具体实施方式
以下结合实施例对本发明作进一步的说明。
实施例1
(1)将60份木质纤维粉碎至粒度为80目的木粉，加入6份硫酸二甲酯和20份聚乙二醇，置于高压反应容器中，在4MPa压力下，反应40min，得到改性木粉；
(2)将20份聚丙烯粒子、5份碱式硫酸镁晶须、5份环磷酰胺和4份对羟基苯丙酮混合搅拌5min；随后经挤出机熔融共混并造粒，得到改性聚丙烯粒子；挤出温度为160℃，螺杆转速30rpm；
(3)将步骤(1)所述改性木粉和步骤(2)所述改性聚丙烯粒子混合，并加入2份偶氮二甲酰胺、1份过氧化二异丙苯、9份4-丁二醇酯和15份丙烯酸，在温度120℃搅拌反应20min；
(4)将步骤(3)所得混合物加入挤出机中，在温度175℃、螺杆转速25rpm下挤出；
(5)随后经模具在温度210℃、压力8MPa下压膜成型；待冷却后即可得到所述耐老化木塑包装材料。
实施例2
(1)将70份木质纤维粉碎至粒度为120目的木粉，加入10份硫酸二甲酯和30份聚乙二醇，置于高压反应容器中，在8MPa压力下，反应30min，得到改性木粉；
(2)将30份聚丙烯粒子、8份碱式硫酸镁晶须、3份环磷酰胺和1份对羟基苯丙酮混合搅拌10min；随后经挤出机熔融共混并造粒，得到改性聚丙烯粒子；挤出温度为180℃，螺杆转速20rpm；
(3)将步骤(1)所述改性木粉和步骤(2)所述改性聚丙烯粒子混合，并加入4份偶氮二甲酰胺、3份过氧化二异丙苯、4份4-丁二醇酯和20份丙烯酸，在温度90℃搅拌反应40min；
(4)将步骤(3)所得混合物加入挤出机中，在温度190℃、螺杆转速45rpm下挤出；
(5)随后经模具在温度190℃、压力12MPa下压膜成型；待冷却后即可得到所述耐老化木塑包装材料。
实施例3
(1)将62份木质纤维粉碎至粒度为100目的木粉，加入8份硫酸二甲酯和26份聚乙二醇，置于高压反应容器中，在6MPa压力下，反应35min，得到改性木粉；
(2)将24份聚丙烯粒子、7份碱式硫酸镁晶须、3份环磷酰胺和4份对羟基苯丙酮混合搅拌6min；随后经挤出机熔融共混并造粒，得到改性聚丙烯粒子；挤出温度为168℃，螺杆转速22rpm；
(3)将步骤(1)所述改性木粉和步骤(2)所述改性聚丙烯粒子混合，并加入3份偶氮二甲酰胺、1份过氧化二异丙苯、8份4-丁二醇酯和17份丙烯酸，在温度100℃搅拌反应28min；
(4)将步骤(3)所得混合物加入挤出机中，在温度180℃、螺杆转速30rpm下挤出；
(5)随后经模具在温度200℃、压力10MPa下压膜成型；待冷却后即可得到所述耐老化木塑包装材料。
实施例4
(1)将68份木质纤维粉碎至粒度为90目的木粉，加入7份硫酸二甲酯和22份聚乙二醇，置于高压反应容器中，在7MPa压力下，反应38min，得到改性木粉；
(2)将28份聚丙烯粒子、6份碱式硫酸镁晶须、5份环磷酰胺和2份对羟基苯丙酮混合搅拌9min；随后经挤出机熔融共混并造粒，得到改性聚丙烯粒子；挤出温度为175℃，螺杆转速27rpm；
(3)将步骤(1)所述改性木粉和步骤(2)所述改性聚丙烯粒子混合，并加入4份偶氮二甲酰胺、3份过氧化二异丙苯、6份4-丁二醇酯和19份 丙烯酸，在温度110℃搅拌反应24min；
(4)将步骤(3)所得混合物加入挤出机中，在温度185℃、螺杆转速40rpm下挤出；
(5)随后经模具在温度205℃、压力12MPa下压膜成型；待冷却后即可得到所述耐老化木塑包装材料。
实施例5
(1)将65份木质纤维粉碎至粒度为90目的木粉，加入8份硫酸二甲酯和28份聚乙二醇，置于高压反应容器中，在6.5MPa压力下，反应35min，得到改性木粉；
(2)将27份聚丙烯粒子、6份碱式硫酸镁晶须、4份环磷酰胺和3份对羟基苯丙酮混合搅拌7min；随后经挤出机熔融共混并造粒，得到改性聚丙烯粒子；挤出温度为175℃，螺杆转速25rpm；
(3)将步骤(1)所述改性木粉和步骤(2)所述改性聚丙烯粒子混合，并加入3份偶氮二甲酰胺、2份过氧化二异丙苯、7份4-丁二醇酯和16份丙烯酸，在温度108℃搅拌反应35min；
(4)将步骤(3)所得混合物加入挤出机中，在温度185℃、螺杆转速35rpm下挤出；
(5)随后经模具在温度200℃、压力10MPa下压膜成型；待冷却后即可得到所述耐老化木塑包装材料。
对上述各个实施例耐老化木塑包装材料性能测试，详细结果见下表：
Figure PCTCN2017112136-appb-000001
Figure PCTCN2017112136-appb-000002
本发明不限于这里的实施例，本领域技术人员根据本发明的揭示，不脱离本发明范畴所做出的改进和修改都应该在本发明的保护范围之内。

Claims (8)

  1. 一种耐老化木塑包装材料的制备方法，其特征在于，包含如下步骤：
    (1)将60-70份木质纤维粉碎至粒度为80-120目的木粉，加入6-10份硫酸二甲酯和20-30份聚乙二醇，置于高压反应容器中，在4-8MPa压力下，反应30-40min，得到改性木粉；
    (2)将20-30份聚丙烯粒子、5-8份碱式硫酸镁晶须、3-5份环磷酰胺和1-4份对羟基苯丙酮混合搅拌5-10min；随后经挤出机熔融共混并造粒，得到改性聚丙烯粒子；
    (3)将步骤(1)所述改性木粉和步骤(2)所述改性聚丙烯粒子混合，并加入2-4份偶氮二甲酰胺、1-3份过氧化二异丙苯、4-9份4-丁二醇酯和15-20份丙烯酸，在温度90-120℃搅拌反应20-40min；
    (4)将步骤(3)所得混合物加入挤出机中，在温度175-190℃、螺杆转速25-45rpm下挤出；
    (5)随后经模具在温度190-210℃、压力8-12MPa下压膜成型；待冷却后即可得到所述耐老化木塑包装材料。
  2. 根据权利要求1所述的一种耐老化木塑包装材料的制备方法，其特征在于，步骤(1)中所述木质纤维为65份、硫酸二甲酯为8份、聚乙二醇28份，在6.5MPa压力下，反应35min。
  3. 根据权利要求1所述的一种耐老化木塑包装材料的制备方法，其特征在于，步骤(2)中所述聚丙烯粒子27份、碱式硫酸镁晶须6份、环磷酰胺4份和对羟基苯丙酮3份混合搅拌7min。
  4. 根据权利要求1所述的一种耐老化木塑包装材料的制备方法，其特征在于，步骤(2)中所述挤出机的挤出温度为160-180℃，螺杆转速20-30rpm。
  5. 根据权利要求1所述的一种耐老化木塑包装材料的制备方法，其特征在 于，步骤(3)中所述偶氮二甲酰胺3份、过氧化二异丙苯2份、4-丁二醇酯7份和丙烯酸16份；在温度108℃搅拌反应35min。
  6. 根据权利要求1所述的一种耐老化木塑包装材料的制备方法，其特征在于，步骤(4)中温度185℃、螺杆转速35rpm。
  7. 根据权利要求1所述的一种耐老化木塑包装材料的制备方法，其特征在于，步骤(5)中所述温度200℃、压力10MPa。
  8. 根据权利要求1-7任意一条所述制备得到的耐老化木塑包装材料。
PCT/CN2017/112136 2017-09-26 2017-11-21 一种耐老化木塑包装材料及其制备方法 WO2019061757A1 (zh)

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