CN113388213B - Polyvinyl chloride foam and preparation method thereof - Google Patents

Polyvinyl chloride foam and preparation method thereof Download PDF

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CN113388213B
CN113388213B CN202110666211.9A CN202110666211A CN113388213B CN 113388213 B CN113388213 B CN 113388213B CN 202110666211 A CN202110666211 A CN 202110666211A CN 113388213 B CN113388213 B CN 113388213B
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silicone oil
polyvinyl chloride
parts
modified silicone
mixture
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CN113388213A (en
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张�成
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Dongying Ruizhi New Material Co ltd
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Dongying Ruizhi New Material Co ltd
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    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—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
    • C08J9/06—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
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    • C08J2203/00—Foams characterized by the expanding agent
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Abstract

The invention belongs to the technical field of PVC materials, and particularly relates to a polyvinyl chloride foam and a preparation method thereof. The polyvinyl chloride foam is prepared from the following raw materials: polyvinyl chloride resin, isocyanate, a foaming agent, acid anhydride, an epoxy compound, modified silicone oil, a plasticizer, an antioxidant, a stabilizer, a filler and a flame retardant; the modified silicone oil is a mixture of any two of sulfhydryl modified silicone oil, amino silicone oil or hydroxyl modified silicone oil, wherein the hydroxyl modified silicone oil is one of phenolic hydroxyl modified silicone oil or alcoholic hydroxyl modified silicone oil. The polyvinyl chloride foam provided by the invention has the advantages that the mechanical property of the prepared PVC foam is fundamentally ensured through the cross-linking reaction of isocyanate, anhydride and epoxy compound; the flame retardant is a mixture of polydimethylsiloxane and antimony trioxide, and the polydimethylsiloxane and the antimony trioxide have a synergistic effect, so that the flame retardance of the prepared PVC foam is ensured.

Description

Polyvinyl chloride foam and preparation method thereof
Technical Field
The invention belongs to the technical field of PVC materials, and particularly relates to a polyvinyl chloride foam and a preparation method thereof.
Background
Polyvinyl chloride (PVC) foam is prepared by taking polyvinyl chloride resin as a main body and adding a foaming agent and other additives, has excellent comprehensive properties such as heat insulation and sound insulation, and is widely applied to the fields of structural parts of airplanes, automobiles, computers and the like, shells of vehicles and ships and the like.
The components of the rigid polyvinyl chloride cross-linked 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, the existing PVC foam cannot have high strength, high thermal stability, flame retardancy and the like at the same time, and the mechanical properties of the PVC foam are reduced after the addition of the related additives, so a novel PVC foam is necessarily sought to achieve relative balance and stability among the properties.
Disclosure of Invention
The purpose of the invention is: a polyvinyl chloride foam and a method for preparing the same are provided. The polyvinyl chloride foam has high thermal stability, mechanical property and flame retardance. The invention also provides a preparation method thereof.
The polyvinyl chloride foam provided by the invention is composed of the following raw materials: polyvinyl chloride resin, isocyanate, a foaming agent, acid anhydride, an epoxy compound, modified silicone oil, a plasticizer, an antioxidant, a stabilizer, a filler and a flame retardant; the modified silicone oil is a mixture of any two of sulfhydryl modified silicone oil, amino silicone oil or hydroxyl modified silicone oil, wherein the hydroxyl modified silicone oil is one of phenolic hydroxyl modified silicone oil or alcoholic hydroxyl modified silicone oil.
Preferably, the polyvinyl chloride foam of the invention comprises the following raw materials in parts by weight: 100 parts of polyvinyl chloride resin, 70-75 parts of isocyanate, 8-10 parts of foaming agent, 35-40 parts of anhydride, 10-12 parts of epoxy compound, 3-5 parts of modified silicone oil, 5-8 parts of plasticizer, 0.3-0.5 part of antioxidant, 4-5 parts of stabilizer, 7-8 parts of filler and 1.5-2.5 parts of flame retardant.
Wherein:
preferably, the modified silicone oil is a mixture of amino silicone oil and hydroxyl modified silicone oil according to the mass ratio of 1:1.
The hydroxyl modified silicone oil mainly utilizes the reactivity of-OH groups to introduce a polysiloxane chain segment into a polymer structure, so that the formability, the demolding property, the smoothness, the heat resistance and the water resistance of the hydroxyl modified silicone oil are greatly improved; the amino modified silicone oil molecule has strong amino polarity, high reactivity, and has adsorptivity, compatibility and easy emulsibility. The thermal decomposition temperature of PVC is improved by adding the modified silicone oil, the thermal stability of the PVC is improved, the mechanical property is not reduced, and the PVC foam has good compatibility and processing fluidity, mainly the bond energy of the Si-O-Si main chain in the introduced modified silicone oil is far higher than that of a C-C bond, and the electronegativity of Si and O atoms is large, so that the prepared PVC foam has good thermal stability.
The polyvinyl chloride resin is formed by combining two resins with similar K values, preferably PVC-SG7 type resin and PVC-SG8 type resin, and the mixing mass ratio of the PVC-SG8 type resin to the PVC-SG7 type resin is 1:1-1: 5.
The isocyanate is one or more of dicyclohexylmethane diisocyanate, carbodiimide modified diphenylmethane diisocyanate, toluene diisocyanate or hexamethylene diisocyanate.
The anhydride is a mixture of maleic anhydride, cyclohexane-1, 2-dicarboxylic anhydride and succinic anhydride.
Wherein: the mass ratio of the maleic anhydride, the cyclohexane-1, 2-dicarboxylic anhydride and the succinic anhydride is 1:1.2-1.5: 0.5-0.8.
The foaming agent is a mixture of azodicarbonamide and biphenyl-4, 4' -disulfonyl azide.
Azodicarbonamide and biphenyl-4, 4 '-disulfonyl azide are used as foaming agents and can be rapidly decomposed in the temperature rising process, and the biphenyl-4, 4' -disulfonyl azide has a certain crosslinking effect, so that the pore size can be reduced and the pore size is uniform while a certain number of pores is ensured, and the high thermal stability of the prepared PVC foam is improved.
The epoxy compound is a mixture of ethylene glycol glycidyl ether and ethylene glycol.
The plasticizer is one or more of diisodecyl adipate, dioctyl azelate or dibutyl sebacate.
The antioxidant is a mixture of phosphite ester and bisphenol A.
The stabilizer is a mixture of zinc stearate and calcium stearate.
The filler is SiC and Al2O3In which SiC and Al2O3The particle size of (A) is 1.0-2.0 microns.
The flame retardant is a mixture of polydimethylsiloxane and antimony trioxide.
The preparation method of the polyvinyl chloride foam comprises the following steps:
(1) weighing the raw materials in parts by weight, and then mechanically mixing to prepare a paste;
(2) injecting the paste prepared in the step (1) into a mold for compression molding, wherein the compression molding pressure is 30MPa, and the temperature is 180 ℃; cooling to room temperature, and opening the mold to obtain a pre-foaming body;
(3) and (3) foaming the pre-foaming body in a water bath environment, and then curing to prepare the polyvinyl chloride foam.
Wherein:
the water bath temperature in the step (3) is 100 ℃, and the curing temperature is 80 ℃.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the polyvinyl chloride foam, the modified silicone oil is added to improve the thermal stability of the prepared PVC foam, the foaming agent is a mixture of azodicarbonamide and biphenyl-4, 4' -disulfonyl azide, the pore size is reduced and the pore uniformity is ensured while the foaming amount is ensured, the modified silicone oil and the foaming agent are compounded to ensure the high thermal stability of the prepared PVC foam, and the micron-sized SiC and Al are added2O3And the PVC resin has good compatibility with PVC resin, and the mechanical property is not reduced while the PVC resin has good high thermal stability.
(2) The polyvinyl chloride foam provided by the invention has the advantages that the mechanical property of the prepared PVC foam is fundamentally ensured through the cross-linking reaction of isocyanate, anhydride and epoxy compound; the flame retardant is a mixture of polydimethylsiloxane and antimony trioxide, and the polydimethylsiloxane and the antimony trioxide have a synergistic effect, so that the flame retardance of the prepared PVC foam is ensured.
(3) The preparation method of the polyvinyl chloride foam has the advantages of wide raw material source, simple process and easily controlled parameters, so that the prepared polyvinyl chloride foam has excellent high thermal stability, mechanical property and flame retardance.
Detailed Description
The present invention is further described below with reference to examples.
Example 1
The polyvinyl chloride foam described in this example 1 is composed of the following raw materials in parts by weight: 100 parts of polyvinyl chloride resin, 75 parts of isocyanate, 10 parts of foaming agent, 38 parts of anhydride, 11 parts of epoxy compound, 5 parts of modified silicone oil, 6.5 parts of plasticizer, 0.4 part of antioxidant, 5 parts of stabilizer, 7.5 parts of filler and 2.0 parts of flame retardant; the modified silicone oil is a mixture of amino silicone oil and phenolic hydroxyl modified silicone oil.
Wherein:
the modified silicone oil is a mixture of amino silicone oil and phenolic hydroxyl modified silicone oil according to the mass ratio of 1:1.
The polyvinyl chloride resin is formed by combining two resins with similar K values, wherein a PVC-SG7 type resin and a PVC-SG8 type resin are selected, and the mixing mass ratio of the PVC-SG8 type resin to the PVC-SG7 type resin is 0.6.
The isocyanate is dicyclohexylmethane diisocyanate.
The anhydride is a mixture of maleic anhydride, cyclohexane-1, 2-dicarboxylic anhydride and succinic anhydride.
Wherein: the mass ratio of the maleic anhydride to the cyclohexane-1, 2-dicarboxylic anhydride to the succinic anhydride is 1:1.5: 0.7.
The foaming agent is a mixture of azodicarbonamide and biphenyl-4, 4' -disulfonyl azide.
Azodicarbonamide and biphenyl-4, 4 '-disulfonyl azide are used as foaming agents and can be rapidly decomposed in the temperature rising process, and the biphenyl-4, 4' -disulfonyl azide has a certain crosslinking effect, so that the pore size can be reduced and the pore size is uniform while a certain number of pores is ensured, and the high thermal stability of the prepared PVC foam is improved.
The epoxy compound is a mixture of ethylene glycol glycidyl ether and ethylene glycol.
The plasticizer is a mixture of diisodecyl adipate and dioctyl azelate.
The antioxidant is a mixture of phosphite ester and bisphenol A.
The stabilizer is a mixture of zinc stearate and calcium stearate.
The filler is SiC and Al2O3In which SiC and Al2O3Has a particle size of 1.0 μm.
The flame retardant is a mixture of polydimethylsiloxane and antimony trioxide.
The preparation method of polyvinyl chloride foam described in this example 1 comprises the following steps:
(1) weighing the raw materials in parts by weight, and then mechanically mixing to prepare a paste;
(2) injecting the paste prepared in the step (1) into a mold for compression molding, wherein the compression molding pressure is 30MPa, and the temperature is 180 ℃; cooling to room temperature, and opening the die to obtain a prefoaming body;
(3) and (3) foaming the pre-foaming body in a water bath environment, and then curing to prepare the polyvinyl chloride foam.
Wherein:
the water bath temperature in the step (3) is 100 ℃, and the curing temperature is 80 ℃.
Example 2
The polyvinyl chloride foam described in this example 2 is composed of the following raw materials in parts by weight: 100 parts of polyvinyl chloride resin, 70 parts of isocyanate, 8 parts of foaming agent, 35 parts of anhydride, 12 parts of epoxy compound, 4 parts of modified silicone oil, 8 parts of plasticizer, 0.3 part of antioxidant, 4 parts of stabilizer, 7 parts of filler and 1.5 parts of flame retardant; the modified silicone oil is a mixture of mercapto modified silicone oil and alcoholic hydroxyl modified silicone oil.
Wherein:
the modified silicone oil is a mixture of mercapto modified silicone oil and alcoholic hydroxyl modified silicone oil according to a mass ratio of 1:1.
The polyvinyl chloride resin is formed by combining two resins with similar K values, wherein a PVC-SG7 type resin and a PVC-SG8 type resin are selected, and the mixing mass ratio of the PVC-SG8 type resin to the PVC-SG7 type resin is 0.2.
The isocyanate is hexamethylene diisocyanate.
The anhydride is a mixture of maleic anhydride, cyclohexane-1, 2-dicarboxylic anhydride and succinic anhydride.
Wherein: the mass ratio of the maleic anhydride to the cyclohexane-1, 2-dicarboxylic anhydride to the succinic anhydride is 1:1.3: 0.7.
The foaming agent is a mixture of azodicarbonamide and biphenyl-4, 4' -disulfonyl azide.
Azodicarbonamide and biphenyl-4, 4 '-disulfonyl azide are used as foaming agents and can be rapidly decomposed in the temperature rising process, and the biphenyl-4, 4' -disulfonyl azide has a certain crosslinking effect, so that the pore size can be reduced and the pore size is uniform while a certain number of pores is ensured, and the high thermal stability of the prepared PVC foam is improved.
The epoxy compound is a mixture of ethylene glycol glycidyl ether and ethylene glycol.
The plasticizer is dibutyl sebacate.
The antioxidant is a mixture of phosphite ester and bisphenol A.
The stabilizer is a mixture of zinc stearate and calcium stearate.
The filler is SiC and Al2O3Mixture of (1), wherein SiC and Al2O3Has a particle size of 1.5 μm.
The flame retardant is a mixture of polydimethylsiloxane and antimony trioxide.
The preparation method of polyvinyl chloride foam described in this example 2 comprises the following steps:
(1) weighing the raw materials in parts by weight, and then mechanically mixing to prepare a paste;
(2) injecting the paste prepared in the step (1) into a mold for compression molding, wherein the compression molding pressure is 30MPa, and the temperature is 180 ℃; cooling to room temperature, and opening the mold to obtain a pre-foaming body;
(3) and (3) foaming the pre-foaming body in a water bath environment, and then curing to prepare the polyvinyl chloride foam.
Wherein:
the water bath temperature in the step (3) is 100 ℃, and the curing temperature is 80 ℃.
Example 3
The polyvinyl chloride foam described in this example 3 is composed of the following raw materials in parts by weight: 100 parts of polyvinyl chloride resin, 73 parts of isocyanate, 9 parts of foaming agent, 40 parts of anhydride, 10 parts of epoxy compound, 3 parts of modified silicone oil, 5 parts of plasticizer, 0.5 part of antioxidant, 5 parts of stabilizer, 8 parts of filler and 2.5 parts of flame retardant; the modified silicone oil is a mixture of mercapto modified silicone oil and phenolic hydroxyl modified silicone oil.
Wherein:
the modified silicone oil is a mixture of amino silicone oil and phenolic hydroxyl modified silicone oil according to a mass ratio of 1:1.
The polyvinyl chloride resin is formed by combining two resins with similar K values, wherein a PVC-SG7 type resin and a PVC-SG8 type resin are selected, and the mixing mass ratio of the PVC-SG8 type resin to the PVC-SG7 type resin is 1.
The isocyanate is carbodiimide modified diphenylmethane diisocyanate.
The anhydride is a mixture of maleic anhydride, cyclohexane-1, 2-dicarboxylic anhydride and succinic anhydride.
Wherein: the mass ratio of the maleic anhydride, the cyclohexane-1, 2-dicarboxylic anhydride and the succinic anhydride is 1:1.2: 0.5.
The foaming agent is a mixture of azodicarbonamide and biphenyl-4, 4' -disulfonyl azide.
Azodicarbonamide and biphenyl-4, 4 '-disulfonyl azide are used as foaming agents and can be rapidly decomposed in the temperature rising process, and the biphenyl-4, 4' -disulfonyl azide has a certain crosslinking effect, so that the pore size can be reduced and the pore size is uniform while a certain number of pores is ensured, and the high thermal stability of the prepared PVC foam is improved.
The epoxy compound is a mixture of glycol glycidyl ether and glycol.
The plasticizer is a mixture of dioctyl azelate and dibutyl sebacate.
The antioxidant is a mixture of phosphite ester and bisphenol A.
The stabilizer is a mixture of zinc stearate and calcium stearate.
The filler is SiC and Al2O3In which SiC and Al2O3Has a particle size of 2.0 μm.
The flame retardant is a mixture of polydimethylsiloxane and antimony trioxide.
The preparation method of polyvinyl chloride foam described in this example 3 comprises the following steps:
(1) weighing the raw materials in parts by weight, and then mechanically mixing to prepare a paste;
(2) injecting the paste prepared in the step (1) into a mold for compression molding, wherein the compression molding pressure is 30MPa, and the temperature is 180 ℃; cooling to room temperature, and opening the mold to obtain a pre-foaming body;
(3) and (3) foaming the pre-foaming body in a water bath environment, and then curing to prepare the polyvinyl chloride foam.
Wherein:
the water bath temperature in the step (3) is 100 ℃, and the curing temperature is 80 ℃.
Comparative example 1
The polyvinyl chloride foam of comparative example 1 is the same as the polyvinyl chloride foam of example 1 in terms of the preparation method, and the only difference is that modified silicone oil is not added to the raw materials, and the foaming agent is azodicarbonamide.
Comparative example 2
The polyvinyl chloride foam of comparative example 2 was prepared in the same manner as the polyvinyl chloride foam of example 1, except that the filler in the raw material was SiC.
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:
TABLE 1 polyvinyl chloride foam Performance test results
Figure BDA0003117524480000061

Claims (6)

1. A polyvinyl chloride foam characterized by: the composite material comprises the following raw materials in parts by weight: 100 parts of polyvinyl chloride resin, 70-75 parts of isocyanate, 8-10 parts of foaming agent, 35-40 parts of anhydride, 10-12 parts of epoxy compound, 3-5 parts of modified silicone oil, 5-8 parts of plasticizer, 0.3-0.5 part of antioxidant, 4-5 parts of stabilizer, 7-8 parts of filler and 1.5-2.5 parts of flame retardant; the modified silicone oil is a mixture of amino silicone oil and hydroxyl modified silicone oil according to a mass ratio of 1:1, wherein the hydroxyl modified silicone oil is one of phenolic hydroxyl modified silicone oil or alcoholic hydroxyl modified silicone oil;
the polyvinyl chloride resin is formed by combining PVC-SG7 type resin and PVC-SG8 type resin, and the mixing mass ratio of the PVC-SG7 type resin to the PVC-SG8 type resin is 1:1-1: 5; the acid anhydride is a mixture of maleic anhydride, cyclohexane-1, 2-dicarboxylic anhydride and succinic anhydride, and the mass ratio of the maleic anhydride to the cyclohexane-1, 2-dicarboxylic anhydride to the succinic anhydride is 1:1.2-1.5: 0.5-0.8;
the epoxy compound is a mixture of ethylene glycol glycidyl ether and ethylene glycol;
the filler is SiC and Al2O3Mixture of (1), wherein SiC and Al2O3The particle size of (A) is 1.0-2.0 microns; the flame retardant is a mixture of polydimethylsiloxane and antimony trioxide.
2. The polyvinyl chloride foam of claim 1, wherein: the isocyanate is one or more of dicyclohexylmethane diisocyanate, carbodiimide modified diphenylmethane diisocyanate, toluene diisocyanate or hexamethylene diisocyanate; the foaming agent is a mixture of azodicarbonamide and biphenyl-4, 4' -disulfonyl azide.
3. The polyvinyl chloride foam of claim 1, wherein: the plasticizer is one or more of diisodecyl adipate, dioctyl azelate or dibutyl sebacate; the antioxidant is a mixture of phosphite ester and bisphenol A.
4. The polyvinyl chloride foam of claim 1, wherein: the stabilizer is a mixture of zinc stearate and calcium stearate.
5. A method of preparing the polyvinyl chloride foam of claim 1, characterized in that: the method comprises the following steps:
(1) weighing the raw materials in parts by weight, and then mechanically mixing to prepare a paste;
(2) injecting the paste prepared in the step (1) into a mold for compression molding, wherein the compression molding pressure is 30MPa, and the temperature is 180 ℃; cooling to room temperature, and opening the die to obtain a prefoaming body;
(3) and (3) foaming the pre-foaming body in a water bath environment, and then curing to prepare the polyvinyl chloride foam.
6. The method for preparing polyvinyl chloride foam according to claim 5, wherein: the water bath temperature in the step (3) is 100 ℃, and the curing temperature is 80 ℃.
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