CN102838816A - New macromolecule fiber composite material - Google Patents

New macromolecule fiber composite material Download PDF

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CN102838816A
CN102838816A CN2012103340025A CN201210334002A CN102838816A CN 102838816 A CN102838816 A CN 102838816A CN 2012103340025 A CN2012103340025 A CN 2012103340025A CN 201210334002 A CN201210334002 A CN 201210334002A CN 102838816 A CN102838816 A CN 102838816A
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parts
agent
composite material
fiber composite
polymer fiber
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CN102838816B (en
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严秀芹
陆绍荣
徐觉明
黄斌
罗崇禧
郭栋
卢李勤
谢超
田卓文
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GUILIN SHUKANG BUILDING MATERIAL CO Ltd
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GUILIN SHUKANG BUILDING MATERIAL CO Ltd
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Abstract

The invention discloses a new macromolecule fiber composite material which is prepared by the following components in parts by weight, 40-100 parts of plant fiberfill, 60-100 parts of plastic base material, 3.5-5 parts of heat stabilizer, 1-2 parts of plasticizer, 1.6-2 parts of lubricating agent, 4-8 parts of modifying agent, 1-3 parts of compatilizer, 2-3 parts of coupling reagent, 1-5 parts of super dispersing agent, 1-4 parts of positive ion surface active agent, 1-1.8 parts of foaming agent, 1-5 parts of blowing promoter, 0.3-1.2 parts of antioxygen, 1-10 parts of cross-linking agent, 1-20 parts of nucleating agent, 0.8-1 part of viscosity reducer, 0.8-1 part of tackifier and 3.2-13.4 parts of other auxiliaries. The new composite material can not easily cause wet swelling and air shrinkage, and is low in expansibility and water absorbability, so that the prepared product has good stability.

Description

novel polymer fiber composite material
Technical Field
The invention relates to the field of polymer materials and products derived from biomass, in particular to a novel polymer fiber composite material.
Background
The novel polymer fiber composite material is a composite material obtained by blending and extruding plant fibers (including wood chips, sisal powder, bagasse, bamboo chips, hemp stems, fruit shells and the like) and plastics, and is widely applied to the fields of civil building decoration, vehicles and ships, national defense and other industries. The material has better processability, has the characteristics of corrosion resistance, attractive appearance, elegance and the like, but has the defect of poor mechanical property, and can be improved by carrying out surface modification on plant fibers and plastics and adding different auxiliaries. The invention patent with publication number CN101921491A discloses a wood-plastic composite material, which comprises 100 parts by weight of wood powder, 20-80 parts by weight of waste plastic, 5-50 parts by weight of waste rubber, 10-60 parts by weight of high-melt-index thermoplastic resin, 1-12 parts by weight of surfactant, 2-8 parts by weight of lubricant, 0.1-4 parts by weight of cross-linking agent, 0.1-4 parts by weight of antioxidant and 0.05-1.5 parts by weight of processing aid; wherein the wood powder has a mesh number of 10 to 325 meshes, the melt flow rate of the high-melt-index thermoplastic resin is more than 20g/10min, and the crosslinking agent is peroxide. The invention improves the dispersibility, the fluidity and the compatibility with plastic of wood powder in the compound by adding high-melt thermoplastic resin and surfactant, and improves the mechanical properties (such as tensile strength, flexural strength, impact strength and the like) of the material by adding waste rubber. However, the rubber is basically from petroleum and belongs to inflammable products, and if the rubber is used on building decoration materials, potential safety hazards exist.
Disclosure of Invention
The invention aims to solve the technical problem of providing a novel polymer fiber composite material which has better mechanical property and lower expansion rate.
The novel polymer fiber composite material is prepared from the following components in parts by weight:
40-100 parts of plant fiber filler; 60-100 parts of plastic base material;
3.5-5 parts of a heat stabilizer; 1-2 parts of a plasticizer;
1.6-2 parts of a lubricant; 4-8 parts of a modifier;
1-3 parts of a compatilizer; 2-3 parts of a coupling agent;
1-5 parts of a hyperdispersant; 1-4 parts of a cationic surfactant;
1-1.8 parts of a foaming agent; 1-5 parts of a foaming auxiliary agent;
0.3-1.2 parts of antioxidant; 1-10 parts of a crosslinking agent;
1-20 parts of a nucleating agent; 0.8-1 part of viscosity reducer;
0.8-1 part of a tackifier; 3.2-13.4 parts of other additives;
wherein,
the heat stabilizer is an organic tin stabilizer, a calcium zinc stabilizer or a lead salt composite stabilizer;
the modifier is ACR-401, ethylene-vinyl acetate copolymer or chlorinated polyethylene;
the cationic surfactant is a quaternary ammonium salt cationic surfactant;
the foaming agent is a combination of sodium bicarbonate and azodicarbonamide or azodiisobutyronitrile in any proportion;
the nucleating agent is one or the combination of more than two of calcium carbonate whisker, nano active light calcium carbonate, talcum powder, titanium dioxide and calcium stearate;
the other auxiliary agents comprise, by weight, 0.5-3 parts of sodium hydroxide, 1-5 parts of urea, 1-3 parts of paraformaldehyde, 0.2-1.2 parts of formic acid and 0.5-1.2 parts of melamine.
The weight parts of the components in the novel polymer fiber composite material are preferably as follows:
50-100 parts of plant fiber filler; 60-80 parts of a plastic base material;
4-5 parts of a heat stabilizer; 1-2 parts of a plasticizer;
1.8-2 parts of a lubricant; 5-7.5 parts of a modifier;
1.5-3 parts of a compatilizer; 2-3 parts of a coupling agent;
2-4 parts of a hyperdispersant; 1-2 parts of a cationic surfactant;
1.2-1.6 parts of a foaming agent; 2-5 parts of a foaming auxiliary agent;
0.5-1 part of antioxidant; 1-5 parts of a crosslinking agent;
5-13 parts of a nucleating agent; 0.8-0.9 part of viscosity reducer;
0.8-0.9 part of tackifier; 4.7-6.7 parts of other additives.
In the above technical scheme:
the plant fiber filler can be fine particles obtained by crushing wood (bamboo) materials such as sawdust, wood shavings, wood chips, coconut shells, bamboo chips or bamboo wool and the like; or fine particles obtained by pulverizing herbal materials such as sisal hemp leftover, sawdust, fruit shell, hemp stalk, peanut shell, chestnut shell, bagasse, etc.; any two or more of the above options may be combined, and the ratio between them may be any ratio. The particle size of the plant fiber filler is usually controlled to be 80-200 meshes.
The plastic substrate may be thermoplastic plastics, such as polyvinyl chloride (PVC), Polyethylene (PE), polypropylene (PP), nylon (PA), Polystyrene (PS), or acrylonitrile-butadiene-styrene copolymer (ABS), etc.; or thermosetting plastics such as amino resin, phenolic resin or epoxy resin; any two or more of the above options may be combined, and the ratio between them may be any ratio. The plastic base material can be a new material or a recycled material, and the granularity of the plastic base material is usually controlled to be 20-100 meshes.
The plasticizer is one or the combination of more than two of dioctyl phthalate, dibutyl phthalate and epoxidized soybean oil; when the plasticizer is a combination of any two or more of the above, the ratio therebetween may be any ratio.
The lubricant is one or the combination of more than two of stearic acid, lead stearate, barium stearate, zinc stearate, paraffin, polyethylene wax and polyethylene oxide wax; when the lubricant is a combination of any two or more of the above, the ratio therebetween may be any ratio.
ACR-401 in the modifier is acrylate high molecular copolymer, and can be produced by Zibo Huaxing assistant Co., Ltd, Zibo hai chemical Co., Ltd, Yu Shang City Yangjiang chemical Co., Ltd and the like.
The compatilizer is polyvinyl lactone, maleic anhydride, acrylic acid or polymethyl propionate.
The coupling agent is one or the combination of more than two of silane coupling agent, titanate coupling agent and aluminate coupling agent. Wherein the silane coupling agent can be r-aminopropyltriethoxysilane (KH550), r-glycidoxypropyltrimethoxysilane (KH560), trifluoropropyltrimethoxysilane (TF3), or heptadecafluorodecyltrimethoxysilane (TF 17); the titanate coupling agent can be a titanate coupling agent NDZ-102, NDZ-201, NDZ-210, NDZ-331 or NDZ-401; the aluminate coupling agent may be aluminate coupling agent DL-441-A, aluminate coupling agent DL-481, or aluminate coupling agent DL-427. When the coupling agent is selected from any two or more of the above combinations, the ratio therebetween may be any ratio.
The hyperdispersant is named as a hyperdispersant, and can be NBZ-3, DA-50, WH-1 or PD-5 hyperdispersant (developed by national superfine powder engineering research center, Shanghai Huaming superfine new material Co., Ltd. and Huadong science and engineering university technical chemistry and physics research institute); or CH series hyperdispersant (Shanghai Sanzheng polymer materials Co., Ltd.); hyperbranched dispersants (developed and produced by the university of Guilin science) are preferably used.
The cationic surfactant is quaternary ammonium salt cationic surfactant, and specifically can be alkyl trimethyl ammonium salt, dialkyl dimethyl ammonium salt or alkyl dimethyl benzyl ammonium salt and the like. The alkyldimethylbenzyl ammonium salt is typically alkyldimethylbenzyl ammonium lauryl sulfate or didecyldimethyl ammonium lauryl sulfate.
The foaming auxiliary agent can be specifically foaming regulator ZB530 (produced by Shandong Huaxing plastic auxiliary agent).
The antioxidant can be 2, 6-di-tert-butyl-p-cresol or tetra [ methyl-beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] pentaerythritol ester.
The cross-linking agent can be benzoyl peroxide, dicumyl peroxide or tert-butyl peroxybenzoate.
The mechanical property of the product can be further improved by adding the nucleating agent, and when the nucleating agent is selected from any two or more of calcium carbonate whisker, nano active light calcium carbonate, talcum powder, titanium dioxide and calcium stearate, the proportion of the nucleating agent can be any proportion.
The polymerization degree of the paraformaldehyde in the processing aid is less than 8, preferably the paraformaldehyde with the polymerization degree of 2-8, specifically can be low-polymerization-degree paraformaldehyde (a glycol polycondensate with the formaldehyde content of 77-93%), and is solid powder (produced by Asahan chemical Co., Ltd., Shandong Shouguang City).
The viscosity reducer is a viscosity reducer LJ-950.
The tackifier is polystyrene resin, monolaurate polyoxyethylene compound or ethylene oxide-propylene oxide block copolymer.
The preparation method of the novel polymer fiber composite material comprises the following steps:
placing the plant fiber filler into a high-speed mixer, adding other auxiliary agents, mixing and stirring for 3-6 min (at the moment, the material temperature reaches 100-120 ℃), opening a hopper cover on the high-speed mixer to diffuse water contained in the plant fiber filler, adding the super-dispersant and the cationic surfactant when the material temperature is reduced to 45-55 ℃, mixing and stirring for 1-2 min, adding the plastic base material and the heat stabilizer when the material temperature is reduced to 55-65 ℃, mixing and stirring for 1-2 min; adding a lubricant, a modifier, a compatilizer, a coupling agent, an antioxidant, a cross-linking agent, a viscosity reducer and a tackifier when the temperature of the material is reduced to 65-75 ℃, mixing and stirring for 2-4 min, adding a plasticizer when the temperature of the material is reduced to 75-85 ℃, mixing and stirring for 2-3 min, adding a foaming agent and a foaming auxiliary agent when the temperature of the material is reduced to 85-95 ℃, mixing and stirring for 2-3 min, adding a nucleating agent when the temperature of the material is reduced to 95-105 ℃, mixing and stirring until the temperature of the material reaches 120 ℃, stopping high-speed mixing, discharging the material, and feeding the obtained premixed material into a single-screw or double-screw granulator for granulation (the processing temperature is 140-170 ℃); and finally, feeding the granules into a single-screw or double-screw extruder (the processing temperature is 150-175 ℃) to extrude various polymer fiber composite new material product blanks, and then carrying out water cooling setting, traction, cutting and blanking to obtain finished products.
The novel polymer fiber composite material provided by the invention is characterized in that other auxiliary agents with special proportions are selected to modify the plant fiber filler, and then the ultra-dispersant, the cationic surfactant and the modified polar groups on the surface of the plant fiber filler are subjected to anchoring effect to reduce the surface polarity of the plant fiber filler, so that on one hand, the novel polymer fiber composite material is beneficial to blending the plant fiber filler and a plastic base material, and the problem of compatibility between the two interfaces is solved; on the other hand, the affinity between the plant fiber filler and the plastic base material can be improved, a compact net structure is formed, the plant fiber filler is dispersed in the composite material more uniformly, the fluidity is better, the stress between the filler and the resin can be well transferred, and the mechanical property of the product is greatly improved. Meanwhile, due to the addition of the hyperdispersant, polar hydroxyl in the modified plant fiber filler is replaced by substituent groups in related auxiliary agents or is coated by a plastic base material, so that the prepared composite material is not easy to generate wet expansion and dry shrinkage, and the expansion rate and the water absorption rate are low, so that the obtained product has better stability; the addition of the cationic surfactant also makes the surface of the extruded product smoother, more beautiful and has better corrosion resistance.
Detailed Description
The present invention is further illustrated by the following specific examples, but the present invention is not limited to these examples.
The following examples were processed as follows:
placing the plant fiber filler into a high-speed mixer, adding other auxiliary agents, mixing and stirring for 5min, then opening a hopper cover on the high-speed mixer to allow water contained in the plant fiber filler to be diffused, adding the hyper-dispersant and the cationic surfactant when the temperature of the material is reduced to 50 ℃, mixing and stirring for 2min, adding the plastic base material and the heat stabilizer when the temperature of the material is reduced to 60 ℃, mixing and stirring for 2 min; adding a lubricant, a modifier, a compatilizer, a coupling agent, an antioxidant, a cross-linking agent, a viscosity reducer and a tackifier when the temperature of the material is reduced to 70 ℃, mixing and stirring for 3min, adding a plasticizer when the temperature of the material is reduced to 80 ℃, mixing and stirring for 3min, adding a foaming agent and a foaming auxiliary agent when the temperature of the material is reduced to 90 ℃, mixing and stirring for 3min, adding a nucleating agent when the temperature of the material is reduced to 100 ℃, mixing and stirring until the temperature of the material reaches 120 ℃, stopping high-speed mixing, discharging the material, and feeding the obtained premixed material into a single-screw or double-screw granulator for granulation (the processing temperature is 140-170 ℃); and finally, feeding the granules into a single-screw or double-screw extruder (the processing temperature is 150-175 ℃) to extrude various polymer fiber composite new material product blanks, and then carrying out water cooling setting, traction, cutting and blanking to obtain finished products.
Example 1
The components were weighed according to the formulation of example 1 in table 1 below and made into a sheet according to the method described above.
Example 2
The components were weighed according to the formulation of example 2 in table 1 below and made into a sheet as described above.
Example 3
The components were weighed according to the formulation of example 3 in table 1 below and made into a sheet as described above.
Example 4
The components were weighed according to the formulation of example 4 in table 1 below and made into a sheet as described above.
Example 5
The components were weighed according to the formulation of example 5 in table 1 below and made into a sheet as described above.
Example 6
The components were weighed according to the formulation of example 6 in table 1 below and made into a sheet as described above.
Table 1:
Figure BDA00002124029100061
Figure BDA00002124029100071
the sheets obtained according to examples 1 to 6 were tested for melt index, flexural strength, tensile strength, impact strength, water absorption and the results are shown in table 2 below:
table 2:
Figure BDA00002124029100072

Claims (9)

1. The new polymer fiber composite material is characterized in that: the composition is prepared from the following components in parts by weight:
40-100 parts of plant fiber filler; 60-100 parts of plastic base material;
3.5-5 parts of a heat stabilizer; 1-2 parts of a plasticizer;
1.6-2 parts of a lubricant; 4-8 parts of a modifier;
1-3 parts of a compatilizer; 2-3 parts of a coupling agent;
1-5 parts of a hyperdispersant; 1-4 parts of a cationic surfactant;
1-1.8 parts of a foaming agent; 1-5 parts of a foaming auxiliary agent;
0.3-1.2 parts of antioxidant; 1-10 parts of a crosslinking agent;
1-20 parts of a nucleating agent; 0.8-1 part of viscosity reducer;
0.8-1 part of a tackifier; 3.2-13.4 parts of other additives;
wherein,
the heat stabilizer is an organic tin stabilizer, a calcium zinc stabilizer or a lead salt composite stabilizer;
the modifier is ACR-401, ethylene-vinyl acetate copolymer or chlorinated polyethylene;
the cationic surfactant is a quaternary ammonium salt cationic surfactant;
the foaming agent is the combination of sodium bicarbonate and azodicarbonamide or azodiisobutyronitrile;
the nucleating agent is one or the combination of more than two of calcium carbonate whisker, nano active light calcium carbonate, talcum powder, titanium dioxide and calcium stearate;
the other auxiliary agents comprise, by weight, 0.5-3 parts of sodium hydroxide, 1-5 parts of urea, 1-3 parts of paraformaldehyde, 0.2-1.2 parts of formic acid and 0.5-1.2 parts of melamine.
2. The new polymer fiber composite material according to claim 1, wherein: the weight parts of each component are as follows:
50-100 parts of plant fiber filler; 60-80 parts of a plastic base material;
4-5 parts of a heat stabilizer; 1-2 parts of a plasticizer;
1.8-2 parts of a lubricant; 5-7.5 parts of a modifier;
1.5-3 parts of a compatilizer; 2-3 parts of a coupling agent;
2-4 parts of a hyperdispersant; 1-2 parts of a cationic surfactant;
1.2-1.6 parts of a foaming agent; 2-5 parts of a foaming auxiliary agent;
0.5-1 part of antioxidant; 1-5 parts of a crosslinking agent;
5-13 parts of a nucleating agent; 0.8-0.9 part of viscosity reducer;
0.8-0.9 part of tackifier; 4.7-6.7 parts of other additives.
3. The novel polymer fiber composite material according to claim 1 or 2, wherein: the plasticizer is one or the combination of more than two of dioctyl phthalate, dibutyl phthalate and epoxidized soybean oil.
4. The novel polymer fiber composite material according to claim 1 or 2, wherein: the lubricant is one or the combination of more than two of stearic acid, lead stearate, barium stearate, zinc stearate, paraffin, polyethylene wax and polyethylene oxide wax.
5. The novel polymer fiber composite material according to claim 1 or 2, wherein: the compatilizer is polyvinyl lactone, maleic anhydride, acrylic acid or polymethyl propionate.
6. The novel polymer fiber composite material according to claim 1 or 2, wherein: the coupling agent is one or the combination of more than two of silane coupling agent, titanate coupling agent and aluminate coupling agent.
7. The novel polymer fiber composite material according to claim 1 or 2, wherein: the cross-linking agent is benzoyl peroxide, dicumyl peroxide or tert-butyl peroxybenzoate.
8. The novel polymer fiber composite material according to claim 1 or 2, wherein: the viscosity reducer is a viscosity reducer LJ-950.
9. The new polymer fiber composite material according to claim 1 or 2, characterized in that: the tackifier is polystyrene resin, monolaurate polyoxyethylene compound or ethylene oxide-propylene oxide block copolymer.
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