CN111607177A - High-strength high-modulus polyvinyl chloride foam and preparation method thereof - Google Patents
High-strength high-modulus polyvinyl chloride foam and preparation method thereof Download PDFInfo
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- CN111607177A CN111607177A CN202010548391.6A CN202010548391A CN111607177A CN 111607177 A CN111607177 A CN 111607177A CN 202010548391 A CN202010548391 A CN 202010548391A CN 111607177 A CN111607177 A CN 111607177A
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- C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
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- C08J2327/00—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 halogen; Derivatives of such polymers
- C08J2327/02—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 halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/04—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 halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08J2327/06—Homopolymers or copolymers of vinyl chloride
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- C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
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- C08K5/15—Heterocyclic compounds having oxygen in the ring
- C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
- C08K5/1515—Three-membered rings
Abstract
The invention belongs to the technical field of polyvinyl chloride foam, and particularly relates to high-strength high-modulus polyvinyl chloride foam. The polyvinyl chloride fiber composite material comprises the following components in parts by weight, wherein the sum of the parts by weight of polyvinyl chloride resin and nylon fiber in the raw materials is 100 parts: 8-10 parts of polyether polyol, 7-10 parts of epoxy compound, 35-75 parts of isocyanate, 22-30 parts of anhydride, 5-10 parts of foaming agent, 15-20 parts of foaming regulator and 3-6 parts of heat stabilizer. The high-strength high-modulus polyvinyl chloride foam disclosed by the invention is high in compression strength and tensile strength, high in elastic modulus and good in thermal stability; the preparation method has the advantages of simple and controllable process, easy construction, easy operation, high production efficiency and suitability for industrial production.
Description
Technical Field
The invention belongs to the technical field of polyvinyl chloride foam, and particularly relates to high-strength high-modulus polyvinyl chloride foam and a preparation method thereof.
Background
The main component of the polyvinyl chloride material is polyvinyl chloride, and other components are added to enhance the heat resistance, toughness, ductility and the like of the polyvinyl chloride material. It is a synthetic material that is enjoyed, popular and widely used in the world today. Its global usage is second highest among various synthetic materials. It is only in 1995 a year that PVC has been statistically produced in europe at around five million tons and consumed at five million thirty million tons. In germany, the production and consumption of PVC averages one hundred and forty million tons, and PVC is being produced and used worldwide at a 4% growth rate.
The components of the rigid polyvinyl chloride crosslinked foam mainly comprise polyvinyl chloride resin, foaming agents (such as azodiisobutyronitrile and azodicarbonamide), isocyanates (such as toluene diisocyanate, carbodiimide-uretonimine modified 4,4' -diphenylmethane diisocyanate) and acid anhydrides (such as maleic anhydride and phthalic anhydride). The preparation method comprises the following steps: firstly mixing solid materials and liquid materials to obtain pasty materials, then pouring the pasty materials into a mold, raising the temperature under pressure to enable the temperature of the pasty materials in the mold to reach 150-200 ℃, at the moment, generating gel on PVC resin, decomposing a foaming agent, controlling the mold pressing time to be 50-60s/mm, cooling, then opening the mold to obtain a pre-foaming body containing a plurality of micro bubbles, finally placing the pre-foaming body in hot water or steam, heating to complete secondary expansion, simultaneously enabling moisture diffused into the pre-foaming body to perform a series of reactions with isocyanate and anhydride to generate carbon dioxide gas and form a cross-linking structure in the foaming body, and curing to obtain the rigid foam.
However, when PVC resin is applied in different environments, the modulus and strength cannot meet the application requirements at the same time, and therefore, it is a technical problem to be solved urgently to explore a PVC foam having both strength and modulus meeting the requirements.
Disclosure of Invention
The purpose of the invention is: a high strength and high modulus polyvinyl chloride foam is provided. The polyvinyl chloride foam has high compression modulus and compressive strength, and the invention also provides a preparation method thereof.
The high-strength high-modulus polyvinyl chloride foam provided by the invention comprises the following components in parts by weight, wherein the sum of the parts by weight of polyvinyl chloride resin and nylon fiber in the raw materials is 100 parts:
wherein:
the weight part ratio of the polyvinyl chloride resin to the nylon fiber is 4: 1-3: 1.
The nylon fiber is a mixture of PA-6, PA-1010 and PA-610, preferably, the mass ratio of PA-6, PA-1010 and PA-610 is 5-8:15-20:30-50, more preferably, the mass ratio of PA-6, PA-1010 and PA-610 is 7:15: 50.
The nylon fiber is ground, and the granularity is controlled to be 180-200 meshes.
The polyether polyol is polyoxypropylene trihydric alcohol which takes glycerol as an initiator, has the primary hydroxyl content of more than or equal to 70 percent, the number average molecular weight of 8500-10000 and is terminated by ethylene oxide.
The epoxy compound is one or two of bisphenol A epoxy resin or epoxidized soybean oil.
The isocyanate is one or more of toluene diisocyanate, cyclohexyl diisocyanate, carbodiimide modified diphenylmethane diisocyanate, diphenylmethane diisocyanate or hexamethylene diisocyanate.
The acid anhydride is at least two of phthalic anhydride, succinic anhydride, trimellitic anhydride, hexachloroendomethyltetrahydrophthalic anhydride, diphenyl ether tetracarboxylic dianhydride, methylhexahydrophthalic anhydride, maleic anhydride, methyltetrahydrophthalic anhydride, cyclohexane-1, 2-dicarboxylic anhydride or methylhexahydrophthalic anhydride.
The blowing agent is a mixture of azodicarbonamide, dimethyl azodiisobutyrate, toluene, cyclohexane and sodium bicarbonate.
The foaming regulator is methyl methacrylate.
The heat stabilizer is a mixture of epoxidized triglyceride, organic tin 181, potassium stearate and calcium stearate.
The preparation method of the high-strength high-modulus polyvinyl chloride foam comprises the following steps:
(1) grinding nylon fibers to 180-mesh 200 meshes, premixing the nylon fibers with liquid materials in the raw materials, standing for 30-35min, adding solid materials, stirring, and stirring the raw materials in a stirrer for 25-35min to obtain uniform premix;
(2) introducing the uniform premix into a mold, performing mold pressing at 165-180 ℃ and under the pressure of 15-20MPa, cooling, and then opening the mold to obtain a pre-foaming body;
(3) placing the pre-foamed body in a water bath environment at the temperature of 90-95 ℃ for foaming to obtain semi-finished foam;
(4) and (3) placing the semi-finished product foam in an oven at 75-80 ℃ for curing treatment to obtain the polyvinyl chloride foam.
Compared with the prior art, the invention has the following beneficial effects:
(1) the high-strength high-modulus polyvinyl chloride foam provided by the invention has the advantages of high compressive strength and tensile strength, high elastic modulus and good thermal stability.
(2) The preparation method of the high-strength high-modulus polyvinyl chloride foam has the advantages of simple and controllable process, easy construction, easy operation and high production efficiency, and is suitable for industrial production.
Detailed Description
The present invention is further described below with reference to examples.
According to the high-strength high-modulus polyvinyl chloride foam, raw materials are mutually matched and have synergistic effect, isocyanate in the raw materials can be used as a plasticizer in the preparation of a pre-foaming body, carbon dioxide is generated as a foaming agent through the reaction of water during secondary expansion and curing crosslinking, and the generated crosslinking substance can reinforce a foam material; the amine generated by isocyanate hydrolysis can generate crosslinking reaction with the crosslinkable polyvinyl chloride resin to obtain the crosslinked polyvinyl chloride resin, thereby improving the dimensional stability and the solvent resistance of the polyvinyl chloride resin.
The acid anhydride can increase the yield of carbon dioxide during curing and crosslinking, improve the foaming ratio and improve a crosslinking network; epoxidized triglycerides in the heat stabilizer improve the toughness and strength of the foam, potassium stearate and calcium stearate improve the quality and heat resistance of the prepared foam material, and reduce the expansion time.
Example 1
The high-strength high-modulus polyvinyl chloride foam described in this example 1 is prepared from the following raw materials in parts by mass:
wherein:
the nylon fiber is a mixture of PA-6, PA-1010 and PA-610, and the mass ratio of the PA-6, the PA-1010 and the PA-610 is 5:15: 35.
The nylon fiber is ground, and the granularity is controlled to be 180 meshes.
The polyether polyol is polyoxypropylene trihydric alcohol which is terminated by ethylene oxide and takes glycerol as an initiator, has the primary hydroxyl content of more than or equal to 80 percent and the number average molecular weight of 9000.
The epoxy compound is bisphenol A epoxy resin.
The isocyanate is a mixture of carbodiimide modified diphenylmethane diisocyanate and hexamethylene diisocyanate.
The anhydride is a mixture of phthalic anhydride, succinic anhydride and maleic anhydride.
The blowing agent is a mixture of azodicarbonamide, dimethyl azodiisobutyrate, toluene, cyclohexane and sodium bicarbonate.
The foaming regulator is methyl methacrylate.
The heat stabilizer is a mixture of epoxidized triglyceride, organic tin 181, potassium stearate and calcium stearate.
The preparation method of the high-strength high-modulus polyvinyl chloride foam described in this embodiment 1 comprises the following steps:
(1) grinding nylon fibers to 180 meshes, premixing the nylon fibers with liquid materials in raw materials, standing for 35min, adding solid materials, stirring, and stirring the raw materials in a stirrer for 30min to obtain uniform premix;
(2) introducing the uniform premix into a mold, molding at 175 deg.C under 18MPa, cooling, and opening the mold to obtain a prefoaming body;
(3) placing the pre-foamed body in a water bath environment at 95 ℃ for foaming to obtain semi-finished foam;
(4) and (3) placing the semi-finished product foam in an oven at 80 ℃ for curing treatment to obtain the polyvinyl chloride foam.
Example 2
The high-strength high-modulus polyvinyl chloride foam described in this example 2 is prepared from the following raw materials in parts by mass:
wherein:
the nylon fiber is a mixture of PA-6, PA-1010 and PA-610, and the mass ratio of the PA-6, the PA-1010 and the PA-610 is 7:15: 50.
The nylon fiber is ground, and the granularity is controlled to be 180 meshes.
The polyether polyol is polyoxypropylene trihydric alcohol which is terminated by ethylene oxide and takes glycerol as an initiator, has the primary hydroxyl content of more than or equal to 80 percent and the number average molecular weight of 8500.
The epoxy compound is a mixture of bisphenol A epoxy resin and epoxidized soybean oil.
The isocyanate is diphenylmethane diisocyanate.
The anhydride is a mixture of diphenyl ether tetracarboxylic dianhydride, maleic anhydride and cyclohexane-1, 2-dicarboxylic anhydride.
The blowing agent is a mixture of azodicarbonamide, dimethyl azodiisobutyrate, toluene, cyclohexane and sodium bicarbonate.
The foaming regulator is methyl methacrylate.
The heat stabilizer is a mixture of epoxidized triglyceride, organic tin 181, potassium stearate and calcium stearate.
The preparation method of the high-strength high-modulus polyvinyl chloride foam described in this embodiment 2 comprises the following steps:
(1) grinding nylon fibers to 200 meshes, premixing the nylon fibers with liquid materials in raw materials, standing for 30min, adding solid materials, stirring, and stirring the raw materials in a stirrer for 35min to obtain uniform premix;
(2) introducing the uniform premix into a mold, performing mold pressing at 180 ℃ and under 20MPa, cooling, and opening the mold to obtain a pre-foaming body;
(3) placing the pre-foamed body in a water bath environment at 90 ℃ for foaming to obtain semi-finished foam;
(4) and (3) placing the semi-finished product foam in an oven at 78 ℃ for curing treatment to obtain the polyvinyl chloride foam.
Example 3
The high-strength high-modulus polyvinyl chloride foam described in this embodiment 3 is prepared from the following raw materials in parts by mass:
wherein:
the nylon fiber is a mixture of PA-6, PA-1010 and PA-610, and the mass ratio of the PA-6, the PA-1010 and the PA-610 is 8:18: 43.
The nylon fiber is ground, and the granularity is controlled to be 200 meshes.
The polyether polyol is polyoxypropylene trihydric alcohol which is terminated by ethylene oxide and takes glycerol as an initiator, has the primary hydroxyl content of more than or equal to 80 percent and the number average molecular weight of 9500.
The epoxy compound is epoxidized soybean oil.
The isocyanate is toluene diisocyanate.
The anhydride is a mixture of trimellitic anhydride and methylhexahydrophthalic anhydride.
The blowing agent is a mixture of azodicarbonamide, dimethyl azodiisobutyrate, toluene, cyclohexane and sodium bicarbonate.
The foaming regulator is methyl methacrylate.
The heat stabilizer is a mixture of epoxidized triglyceride, organic tin 181, potassium stearate and calcium stearate.
The preparation method of the high-strength high-modulus polyvinyl chloride foam described in this embodiment 3 comprises the following steps:
(1) grinding nylon fibers to 200 meshes, premixing the nylon fibers with liquid materials in raw materials, standing for 33min, adding solid materials, stirring, and stirring the raw materials in a stirrer for 35min to obtain uniform premix;
(2) introducing the uniform premix into a mold, molding at 185 deg.C under 20MPa, cooling, and opening the mold to obtain a prefoaming body;
(3) placing the pre-foamed body in a water bath environment at 93 ℃ for foaming to obtain semi-finished foam;
(4) and (3) placing the semi-finished product foam in an oven at 80 ℃ for curing treatment to obtain the polyvinyl chloride foam.
Comparative example 1
The polyvinyl chloride foam of comparative example 1 is prepared from the following raw materials in parts by mass:
wherein:
the polyether polyol is polyoxypropylene trihydric alcohol which is terminated by ethylene oxide and takes glycerol as an initiator, has the primary hydroxyl content of more than or equal to 80 percent and the number average molecular weight of 8500.
The epoxy compound is a mixture of bisphenol A epoxy resin and epoxidized soybean oil.
The isocyanate is diphenylmethane diisocyanate.
The anhydride is a mixture of diphenyl ether tetracarboxylic dianhydride, maleic anhydride and cyclohexane-1, 2-dicarboxylic anhydride.
The blowing agent is a mixture of azodicarbonamide, dimethyl azodiisobutyrate, toluene, cyclohexane and sodium bicarbonate.
The foaming regulator is methyl methacrylate.
The heat stabilizer is a mixture of epoxidized triglyceride, organic tin 181, potassium stearate and calcium stearate.
The preparation method described in this comparative example 1 is the same as that of example 2.
Comparative example 2
The polyvinyl chloride foam of comparative example 2 is prepared from the following raw materials in parts by mass:
wherein:
the nylon fiber is a mixture of PA-6, PA-1010 and PA-610, and the mass ratio of the PA-6, the PA-1010 and the PA-610 is 7:15: 50.
The nylon fiber is ground, and the granularity is controlled to be 180 meshes.
The polyether polyol is polyoxypropylene trihydric alcohol which is terminated by ethylene oxide and takes glycerol as an initiator, has the primary hydroxyl content of more than or equal to 80 percent and the number average molecular weight of 8500.
The epoxy compound is a mixture of bisphenol A epoxy resin and epoxidized soybean oil.
The isocyanate is diphenylmethane diisocyanate.
The anhydride is a mixture of diphenyl ether tetracarboxylic dianhydride, maleic anhydride and cyclohexane-1, 2-dicarboxylic anhydride.
The blowing agent is a mixture of azodicarbonamide, dimethyl azodiisobutyrate, toluene, cyclohexane and sodium bicarbonate.
The foaming regulator is methyl methacrylate.
The heat stabilizer is organic tin 181.
The preparation method described in this comparative example 2 is the same as that of example 2.
The polyvinyl chloride foams prepared in examples 1 to 3 and comparative examples 1 to 2 were subjected to the performance test, and the results are shown in the following table 1:
Claims (10)
1. a high-strength high-modulus polyvinyl chloride foam is characterized in that: the polyvinyl chloride fiber composite material comprises the following components in parts by weight, wherein the sum of the parts by weight of polyvinyl chloride resin and nylon fiber in the raw materials is 100 parts:
2. the high strength high modulus polyvinyl chloride foam according to claim 1, wherein: the weight part ratio of the polyvinyl chloride resin to the nylon fiber is 4: 1-3: 1; the nylon fiber is a mixture of PA-6, PA-1010 and PA-610, and the nylon fiber is ground and has a particle size controlled at 180-200 meshes.
3. The high strength high modulus polyvinyl chloride foam according to claim 2, wherein: the mass ratio of the PA-6 to the PA-1010 to the PA-610 is 5-8:15-20: 30-50.
4. The high strength high modulus polyvinyl chloride foam according to claim 1, wherein: the polyether polyol is polyoxypropylene trihydric alcohol which takes glycerol as an initiator, has the primary hydroxyl content of more than or equal to 70 percent, the number average molecular weight of 8500-10000 and is terminated by ethylene oxide.
5. The high strength high modulus polyvinyl chloride foam according to claim 1, wherein: the epoxy compound is one or two of bisphenol A epoxy resin or epoxidized soybean oil.
6. The high strength high modulus polyvinyl chloride foam according to claim 1, wherein: the isocyanate is one or more of toluene diisocyanate, cyclohexyl diisocyanate, carbodiimide modified diphenylmethane diisocyanate, diphenylmethane diisocyanate or hexamethylene diisocyanate.
7. The high strength high modulus polyvinyl chloride foam according to claim 1, wherein: the acid anhydride is at least two of phthalic anhydride, succinic anhydride, trimellitic anhydride, hexachloroendomethyltetrahydrophthalic anhydride, diphenyl ether tetracarboxylic dianhydride, methylhexahydrophthalic anhydride, maleic anhydride, methyltetrahydrophthalic anhydride, cyclohexane-1, 2-dicarboxylic anhydride or methylhexahydrophthalic anhydride.
8. The high strength high modulus polyvinyl chloride foam according to claim 1, wherein: the foaming agent is a mixture of azodicarbonamide, dimethyl azodiisobutyrate, toluene, cyclohexane and sodium bicarbonate; the foaming regulator is methyl methacrylate.
9. The high strength high modulus polyvinyl chloride foam according to claim 1, wherein: the heat stabilizer is a mixture of epoxidized triglyceride, organic tin 181, potassium stearate and calcium stearate.
10. A method for preparing a high strength high modulus polyvinyl chloride foam according to claim 1, wherein: the method comprises the following steps:
(1) grinding nylon fibers to 180-mesh 200 meshes, premixing the nylon fibers with liquid materials in the raw materials, standing for 30-35min, adding solid materials, stirring, and stirring the raw materials in a stirrer for 25-35min to obtain uniform premix;
(2) introducing the uniform premix into a mold, performing mold pressing at 165-180 ℃ and under the pressure of 15-20MPa, cooling, and then opening the mold to obtain a pre-foaming body;
(3) placing the pre-foamed body in a water bath environment at the temperature of 90-95 ℃ for foaming to obtain semi-finished foam;
(4) and (3) placing the semi-finished product foam in an oven at 75-80 ℃ for curing treatment to obtain the polyvinyl chloride foam.
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| CN104672706A (en) * | 2015-02-13 | 2015-06-03 | 中国科学院长春应用化学研究所 | Suspension PVC (Polyvinyl Chloride) resin-based foaming material and preparation method thereof |
| CN109054234A (en) * | 2018-07-12 | 2018-12-21 | 洛阳科博思新材料科技有限公司 | Flame-proof heat-resistant polyvinyl chloride structural foam material of high specific strength and preparation method thereof |
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| CN104672706A (en) * | 2015-02-13 | 2015-06-03 | 中国科学院长春应用化学研究所 | Suspension PVC (Polyvinyl Chloride) resin-based foaming material and preparation method thereof |
| CN109054234A (en) * | 2018-07-12 | 2018-12-21 | 洛阳科博思新材料科技有限公司 | Flame-proof heat-resistant polyvinyl chloride structural foam material of high specific strength and preparation method thereof |
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