CN110982189A - PVC structural foam and preparation method thereof - Google Patents

PVC structural foam and preparation method thereof Download PDF

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Publication number
CN110982189A
CN110982189A CN201911104342.7A CN201911104342A CN110982189A CN 110982189 A CN110982189 A CN 110982189A CN 201911104342 A CN201911104342 A CN 201911104342A CN 110982189 A CN110982189 A CN 110982189A
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parts
pvc
structural foam
curing agent
resin
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CN110982189B (en
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谢映雪
刘芳
何经纬
李永鸿
李爽
招炳健
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South China University of Technology SCUT
FSPG Hi Tech Co Ltd
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South China University of Technology SCUT
FSPG Hi Tech Co Ltd
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    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/06Working-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
    • C08J9/10Working-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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    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
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    • C08J9/06Working-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
    • C08J9/10Working-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
    • C08J9/104Hydrazines; Hydrazides; Semicarbazides; Semicarbazones; Hydrazones; Derivatives thereof
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    • C08J2327/00Characterised 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
    • C08J2327/02Characterised 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
    • C08J2327/04Characterised 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
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    • C08K7/22Expanded, porous or hollow particles
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    • C08K7/26Silicon- containing compounds

Abstract

The invention discloses PVC structural foam which comprises the following raw material components in parts by weight: 100 parts of PVC resin, 5-80 parts of epoxy resin, 0.4-24 parts of epoxy curing agent, 5-20 parts of foaming agent, 3-20 parts of sensitizer, 1-8 parts of stabilizer and 5-15 parts of processing aid. According to the invention, through special setting of raw material components and proportion, an epoxy resin crosslinking system is introduced, so that the epoxy resin crosslinking system and a PVC resin crosslinking system form a double crosslinking system with two resin systems interpenetrating after irradiation foaming, on the basis of ensuring the uniformity of the PVC crosslinking system and obtaining foam with fine and uniform pores, high closed pore rate and low water absorption, the rigidity of a crosslinking structure is enhanced by using the epoxy resin system, and the crosslinking density and crosslinking strength of the whole system are greatly improved, thereby greatly improving the mechanical property and heat resistance of the prepared structural foam. The invention also discloses a preparation method of the PVC structural foam.

Description

PVC structural foam and preparation method thereof
Technical Field
The invention relates to the field of structural foam, in particular to PVC structural foam.
Background
The sandwich structure composite material taking the PVC structure foam as the core material has the characteristics of high strength, light weight and the like, can be widely applied to the fields of wind power generation, ships, aerospace, rail transit and the like with high requirements on strength and weight reduction, and can meet the requirements of the fields on weight reduction, energy conservation and the like. To prepare rigid PVC foams with high expansion ratios, the problem of too low melt strength of PVC at high temperatures (during foaming) needs to be solved, while the two conflicting performance requirements of low density and high strength are often the most difficult problems to solve for structural foams. In order to solve the problems of low strength and high foaming ratio of PVC melt and realize light weight and high strength, a chemical method and an irradiation crosslinking method can be adopted.
PVC structural foam products in the market mainly adopt a chemical method, namely, isocyanate, anhydride and the like are added into PVC to form a cross-linking system with double polymer components, for example, an improved cross-linked polyvinyl chloride structural foam disclosed in Chinese patent 200910033041.X and a preparation method thereof can be used for preparing the PVC structural foam with low density (60-130 kg/m)3) High strength and good heat resistance. The chemical method for producing PVC structural foam has the problems of long process flow, poor controllability, high energy consumption and high cost, and the produced foam also has the problems of thick foam holes, high water absorption, easy powder falling and the like which are not beneficial to downstream application. The method adopts isocyanate, anhydride and the like to form a crosslinking system to modify PVC, the pore diameter of a cell formed by the system is larger, so that the water absorption rate is higher, and the system formed by the isocyanate has the problem of easy powder falling, so that the performance and the strength of the foam and other materials during composite molding are influenced.
The irradiation crosslinking method is a method of adding an irradiation sensitizer in the formula, forming a proper crosslinking structure after irradiation to ensure the melt strength during PVC foaming, and preparing light high-strength PVC structural foam, such as a radiation crosslinking PVC rigid foaming material disclosed in Chinese patent 201010171364.8, which can be used for preparing a PVC rigid foaming material with low density (60-130 kg/m)3) The method has the advantages of simple process equipment, strong controllability and low cost, and the prepared foam has fine and uniform foam holes, low resin absorption rate and no powder falling and can well solve the problems of the chemical method. However, the irradiation crosslinking method adopts a pure PVC resin system, so that the rigidity of the formed crosslinking structure is not strong enough, the foam is easy to soften when heated to more than 80 ℃, and the heat resistance of the prepared foam is poorer than that of the chemical method, thereby influencing the application of the foam in the field with higher composite molding temperature. Therefore, in order to widen the application field of the foams prepared by the irradiation crosslinking method, the heat-resistant modification of the foams is urgently needed. The methods adopted in the prior art comprise adding a reinforcing modifier, adding a sensitizer containing a rigid structure (such as Chinese patent 201210491495.3), and performing secondary crosslinking by subsequent silane coupling agent treatment, but only one of the reinforcing modifier, the sensitizer and the PVC resin has limited addition amount and compatibility with the modified additiveThe mechanical property and the heat resistance of the foam are improved to a certain degree, but the use requirements of high-end products such as wind power blades and the like cannot be met.
Disclosure of Invention
The invention aims to provide PVC structural foam and a preparation method thereof, aiming at the defects of the prior art.
The technical scheme adopted by the invention is as follows: a PVC structural foam comprises the following raw material components in parts by weight: 100 parts of PVC resin, 5-80 parts of epoxy resin, 0.4-24 parts of epoxy curing agent, 5-20 parts of foaming agent, 3-20 parts of sensitizer, 1-8 parts of stabilizer and 5-15 parts of processing aid.
Specifically, on the basis of preparing PVC structural foam by an irradiation crosslinking method, an epoxy resin system with better heat resistance is introduced into a formula to form two crosslinking systems, namely a PVC resin irradiation crosslinking system and an epoxy resin crosslinking system interpenetrating double crosslinking system are formed, and on the basis of retaining the advantages of uniform crosslinking, fine and uniform foam pores, low water absorption and the like of the PVC resin irradiation crosslinking system, the crosslinking structure of the epoxy resin is utilized to form a powerful support for the whole system, so that the crosslinking density and crosslinking strength of the whole system are improved, and the aims of improving the mechanical property and heat resistance of the PVC structural foam are fulfilled.
In order to obtain a composition using an epoxy resin and a PVC resin as a main resin, the range of a compatibility interval between the epoxy resin and the PVC resin needs to be studied, and thus the type and the addition amount of the epoxy resin have a critical influence on the processability and foaming effect of forming an interpenetrating double-crosslinked system. As a further improvement of the scheme, the PVC structural foam comprises the following raw material components in parts by weight: 100 parts of PVC resin, 10-80 parts of epoxy resin, 0.8-24 parts of epoxy curing agent, 5-20 parts of foaming agent, 3-20 parts of sensitizer, 1-8 parts of stabilizer and 5-15 parts of processing aid. Actually, epoxy resin has been used as one of raw material components of PVC resin compositions in the prior art due to its good heat resistance, however, due to the compatibility problem of epoxy resin and PVC resin, the difficulty of controllability of post foaming processing is greatly increased, so that the prior art only can add a small amount of epoxy resin and introduce a coupling agent, which is an attempt to overcome the technical problem, but the final performance of the product is still to be improved due to the insufficient addition amount of epoxy resin. According to the invention, the epoxy resin and the PVC resin are used as the main resin, namely, the addition amount of the epoxy resin is greatly increased, and the modification difficulty of the whole resin system is greatly increased, so that the specific selection and addition amount of the epoxy resin, the specific selection and addition amount of the epoxy curing agent and the setting of each raw material component in the whole formula are particularly important.
As a further improvement of the scheme, the epoxy value of the epoxy resin is 0.05-0.51 mol/100 g. Specifically, the epoxy value is too high, the activity is relatively high, and a crosslinked network is easily formed, so that foaming and formation of another crosslinked network are inhibited; if the epoxy value is too low, the activity ratio of epoxy groups is low, and an effective crosslinking structure is difficult to form, so that the crosslinking strength of the system is difficult to effectively support.
As a further improvement of the scheme, the epoxy curing agent is selected from at least one of dicyandiamide, maleic anhydride, phthalic anhydride, SH-201 curing agent and SH-200 curing agent. Particularly, the dicyandiamide, the maleic anhydride, the benzoic anhydride, the SH-201 curing agent and the SH-200 curing agent are all suitable for completely curing at one time, and the dicyandiamide, the maleic anhydride, the benzoic anhydride, the SH-201 curing agent and the SH-200 curing agent can obtain a good curing effect when compounded with the epoxy resin. As a further improvement of the above scheme, the invention preferably selects SH-201 curing agent or SH-200 curing agent and the combination of the two curing agents and one of dicyandiamide, maleic anhydride and phthalic anhydride. The SH-201 curing agent and the SH-200 curing agent have special complete secondary curing functions, namely, the SH-201 curing agent and the SH-200 curing agent are uniformly mixed with the epoxy resin to perform primary curing at a lower temperature, so that the mixture is not completely cured to form primary crosslinking, and then the mixture is uniformly mixed with the PVC resin system to perform secondary curing under a foaming condition, so that the mixture is completely cured to form secondary crosslinking.
As a further improvement of the above aspect, the foaming agent is at least one selected from the group consisting of azodicarbonamide (AC foaming agent), trihydrazino-s-triazine (THT), N-nitroguanidine, p-methylsulfonylurea, and phenyltetrazole. Specifically, the decomposition temperature of the blowing agent of the present invention needs to be higher than the molding temperature of the PVC resin and not so high as to cause a large amount of decomposition of the PVC resin.
As a further improvement of the above scheme, the sensitizer is at least one selected from the group consisting of trimethylolpropane triacrylate (TMPTA), trimethylolpropane trimethacrylate (TMPTMA), Divinylbenzene (DVB), N '-4, 4' -diphenylmethane bismaleimide, and triallyl isocyanate (TAIC).
The further improvement of the scheme is that the composite material further comprises 0-10 parts of a plasticizer, 0-2 parts of an activating agent, 0-5 parts of a lubricant and 0-20 parts of an inorganic filler in parts by weight of raw materials.
As a further improvement of the above scheme, the activating agent is at least one selected from zinc stearate, calcium stearate, zinc oxide and urea. Specifically, the present invention incorporates an activator to adjust the decomposition temperature of the blowing agent to match the PVC resin and epoxy resin double cross-linked system of the present invention.
In addition, the formula of the invention has no special requirements on the stabilizer, the processing aid, the plasticizer and the lubricant, and can select and use the raw materials commonly used in the processing process of the PVC resin foaming system, wherein the plasticizer, the activator, the lubricant and the inorganic filler are selected according to the requirements of specific finished products, whether the plasticizer, the activator, the lubricant and the inorganic filler are added or not and the addition amount of the plasticizer, the activator, the lubricant and the inorganic filler is also selected according.
The preparation method of the PVC structural foam comprises the following process steps:
1) uniformly mixing and curing epoxy resin and an epoxy curing agent according to the weight parts of the raw materials, uniformly mixing the epoxy resin and the epoxy curing agent with PVC resin, sequentially adding the raw material components except the epoxy resin and the epoxy curing agent, stirring the raw material components at a high speed to 80-110 ℃, then stirring the raw material components at a low speed to 40 ℃, and then mixing, pressing and forming the raw material components and cooling the raw material components to obtain a semi-finished plate;
2) carrying out irradiation crosslinking on the semi-finished plate obtained in the step 1) and then carrying out foaming treatment to obtain a finished product.
Specifically, the preparation method adopts the methods of epoxy resin curing crosslinking and PVC resin irradiation crosslinking to form a double-crosslinking system with two interpenetrating resin systems, so that the melt strength of the PVC resin composition during foaming is improved, and the PVC structural foam with more excellent comprehensive performance is obtained. Because the irradiation crosslinking mode of the PVC resin is not changed in the preparation process, the uniformity of a PVC resin crosslinking system can be ensured, and thus, the prepared foam has the advantages of fine and uniform foam holes, high closed-cell rate, low water absorption rate and the like. Meanwhile, on the basis, the crosslinking density and the crosslinking strength of the whole system are improved by adopting a mode of enhancing the crosslinking structure by the reaction of the epoxy resin and the epoxy curing agent, so that the mechanical property and the heat resistance of the prepared structural foam are improved. In addition, the addition of the epoxy resin has a certain plasticizing effect on the PVC resin, and the processing performance of the whole formula system can be improved. In fact, the preparation method of the invention adopts irradiation crosslinking to greatly improve the melt strength of PVC resin, so as to prepare foam with high foaming ratio, wherein the foaming ratio reaches 10-25 times, and the intermolecular acting force is greatly reduced due to the high foaming ratio, so that the difficulty of heat-resistant modification of PVC structural foam is greatly increased. Meanwhile, tests show that the charging sequence of the epoxy resin has a great influence on the compatibility and the foaming effect of the whole system. The epoxy curing agent and the epoxy resin are uniformly mixed, then the mixture is uniformly mixed with the PVC resin, and other additives are added, so that the mixing uniformity and compatibility of the system can be ensured. If the PVC resin and other additives are uniformly mixed and then the epoxy resin is added, the technical problems that the compatibility of the epoxy resin and a system is poor, the epoxy resin is easy to separate out from the system and the foaming is failed occur, or the technical problems of uneven dispersion, incomplete curing and the like also occur when the epoxy curing agent and the epoxy resin are directly added into the PVC resin system respectively. Therefore, the feeding sequence in the preparation process is particularly important for the comprehensive performance of the final product, and the subsequent irradiation crosslinking and heating foaming procedures are combined, so that a double-crosslinking system with interpenetrating epoxy resin systems and PVC resin systems is favorably formed, and the mechanical property and the heat resistance of the PVC structural foam are greatly improved.
Furthermore, the epoxy curing agent in the preparation process can adopt an epoxy curing agent which is completely cured once, and can also adopt a secondary curing epoxy curing agent which is beneficial to further improving the comprehensive performance of the PVC structural foam. The epoxy curing agent with complete primary curing can be one of dicyandiamide, maleic anhydride, phthalic anhydride, SH-201 curing agent and SH-200 curing agent, and the epoxy curing agent with complete secondary curing can be SH-201 curing agent or SH-200 curing agent. When the SH-201 curing agent or the SH-200 curing agent is selected as the epoxy curing agent, the epoxy curing agent needs to be uniformly mixed with the epoxy resin for primary curing, so that the epoxy curing agent is not completely cured to form primary crosslinking, the epoxy curing agent is ground and then mixed with the PVC resin and other raw material components, secondary curing is completely carried out under the foaming condition, and the rest steps are the same as the steps of selecting the epoxy curing agent completely cured for the primary curing. The epoxy curing agent for secondary curing is utilized to perform semi-complete curing and complete curing at different temperatures, so that an epoxy resin system can form a more excellent rigid structure, and the mechanical property and the heat resistance of the whole resin system are further improved.
As a further improvement of the scheme, in the step 2), the irradiation crosslinking foaming treatment is to perform irradiation of a cobalt source or an electron beam with the irradiation dose of 4-80 kGy, and then foam in a mould pressing or hot air mode, wherein the foaming temperature is controlled to be 175-210 ℃, and the treatment time is 4-30 min. In fact, in order to ensure that the foaming agent is not decomposed in advance when the plate is formed, a high-temperature foaming agent is required; PVC is easily decomposed at high temperature, and the temperature and time during foaming are strictly controlled.
The invention has the beneficial effects that:
according to the invention, through special setting of raw material components and proportion, an epoxy resin crosslinking system is introduced, so that the epoxy resin crosslinking system and a PVC resin crosslinking system form a double crosslinking system with two resin systems interpenetrating after irradiation foaming, on the basis of ensuring the uniformity of the PVC crosslinking system and obtaining foam with fine and uniform pores, high closed pore rate and low water absorption, the rigidity of a crosslinking structure is enhanced by using the epoxy resin system, and the crosslinking density and crosslinking strength of the whole system are improved, thereby greatly improving the mechanical property and heat resistance of the prepared structural foam.
The preparation method provided by the invention has strong controllability, and through special setting of the feeding sequence and the curing process, a plurality of technical problems of compatibility, uneven dispersion, incomplete curing and the like of raw material components in the PVC resin composition are solved, and the heat resistance and the mechanical property of the PVC high-foaming-rate foam are successfully modified.
Detailed Description
The present invention is specifically described below with reference to examples in order to facilitate understanding of the present invention by those skilled in the art. It should be particularly noted that the examples are given solely for the purpose of illustration and are not to be construed as limitations on the scope of the invention, as non-essential improvements and modifications to the invention may occur to those skilled in the art, which fall within the scope of the invention as defined by the appended claims. Meanwhile, the raw materials mentioned below are not specified in detail and are all commercial products; the process steps or preparation methods not mentioned in detail are all process steps or preparation methods known to the person skilled in the art.
Example 1
The PVC structural foam of the embodiment comprises the following raw materials in parts by weight:
Figure BDA0002270827180000051
the preparation method comprises the following steps:
1) uniformly mixing the epoxy resin SH-E50 with the epoxy value of 0.12 and dicyandiamide serving as an epoxy curing agent according to the weight parts of the raw materials, uniformly mixing the mixture with PVC resin, sequentially adding other raw material components, stirring the mixture at a high speed to 100 ℃, stirring the mixture at a low speed to 40 ℃, and then mixing, pressing and molding the mixture by using an open mill at 130 ℃ to obtain a semi-finished plate;
2) irradiating the semi-finished plate obtained in the step 1) by using a cobalt source to 14kGy, foaming by using hot air at 175 ℃ for 30min, cooling and shaping to obtain the PVC structural foam finished product of the example 1.
The detection proves that the compression strength of the finished product of the example 1 is 1.07MPa, the Martin heat-resistant temperature is 90.5 ℃, and the water absorption is 1.5%.
Comparative example 1
The PVC structural foam of the comparative example comprises the following raw materials in parts by weight:
Figure BDA0002270827180000061
the preparation method comprises the following steps:
1) mixing the raw material components in parts by weight at a high speed, then placing the mixture in an internal mixer for internal mixing for 10min at 160 ℃, granulating, and then placing the mixture in an extruder for extruding a semi-finished plate;
2) irradiating the semi-finished plate obtained in the step 1) by using an electron accelerator, controlling the dose to be 80kGy and the irradiation speed to be 10m/min, then carrying out oil bath foaming at 195 ℃ for 10min, cooling and shaping, and preparing the PVC structural foam finished product of the comparative example 1.
The compression strength of the finished product of the comparative example 1 is 0.91MPa and the Martin heat-resistant temperature is 82.5 ℃ through detection. As can be seen from the raw material ratio and the preparation method of the comparative example 1 and the comparative example 1, even if ABS is added in the comparative example 1 to modify a PVC resin system and the heat-resistant modifier X-1202 is added, after the PVC structural foam is prepared by a common irradiation crosslinking foaming process, PVC structural foam with excellent heat resistance and high compression strength cannot be obtained.
Comparative example 2
The PVC structural foam of the comparative example comprises the following raw materials in parts by weight:
Figure BDA0002270827180000062
Figure BDA0002270827180000071
the preparation method comprises the following steps:
1) mixing the raw material components in parts by weight at a high speed, stirring at a low temperature, cooling to 40 ℃, then placing the mixture into an internal mixer to be internally mixed for 10min at 150 ℃, and then calendering to obtain a semi-finished plate;
2) irradiating the semi-finished plate obtained in the step 1) by using an electron accelerator, controlling the dose to be 70kGy and the irradiation speed to be 10m/min, then foaming for 7min by using a salt bath at 220 ℃, removing surface salt in a water bath at 60 ℃, and drying by using a blast oven to obtain the PVC structural foam finished product in the comparative example 2.
The compression strength of the finished product of the comparative example 2 is 0.88MPa, and the Martin heat-resistant temperature is 80.3 ℃. It can be seen from the raw material ratio and the preparation method of comparative example 1 and comparative example 2 that even though the composite stabilizer and various functional additives are added in the comparative example 2 to modify the PVC resin system, the PVC structural foam with excellent heat resistance and high compressive strength cannot be obtained after the PVC resin system is prepared by the common irradiation crosslinking foaming process.
Comparative example 3
The PVC structural foam of the embodiment comprises the following raw materials in parts by weight:
Figure BDA0002270827180000072
the preparation method comprises the following steps:
1) uniformly mixing epoxy resin with an epoxy value of 0.54 and dicyandiamide as an epoxy curing agent according to the weight parts of the raw materials, uniformly mixing the mixture with PVC resin, sequentially adding other raw material components, stirring the mixture at a high speed to 100 ℃, then stirring the mixture at a low speed to 40 ℃, and then mixing, pressing and molding the mixture by using an open mill at a temperature of 130 ℃ and cooling the mixture to obtain a semi-finished plate;
2) irradiating the semi-finished plate obtained in the step 1) by using a cobalt source to 14kGy, and then foaming by using hot air at 175 ℃ for 30 min.
This is because the epoxy resin is cured by reaction in advance, which hinders the uniformity of crosslinking of the entire system.
Example 2
The PVC structural foam of the embodiment comprises the following raw materials in parts by weight:
Figure BDA0002270827180000081
the preparation method comprises the following steps:
1) uniformly mixing epoxy resin with an epoxy value of 0.05 and an SH-201 curing agent according to the weight parts of the raw materials, uniformly mixing the mixture with PVC resin, sequentially adding other raw material components, stirring the mixture at a high speed to 100 ℃, then stirring the mixture at a low speed to 40 ℃, and then mixing, pressing and molding the mixture by using an open mill at 145 ℃ to obtain a semi-finished plate;
2) irradiating the semi-finished plate obtained in the step 1) by using a cobalt source for 4kGy, carrying out mould pressing foaming at 200 ℃ and 11MPa for 13min, and cooling and shaping to obtain the PVC structural foam finished product of the example 2.
The detection proves that the compression strength of the finished product of the example 2 is 1.16MPa, the Martin heat-resisting temperature is 91.8 ℃, and the water absorption is 1.3%.
Example 3
The PVC structural foam of the embodiment comprises the following raw materials in parts by weight:
Figure BDA0002270827180000082
Figure BDA0002270827180000091
the preparation method comprises the following steps:
1) uniformly mixing the epoxy resin E51 and the SH-201 curing agent according to the weight parts of the raw materials, then uniformly mixing the mixture with the PVC resin, sequentially adding other raw material components, stirring the mixture at a high speed to 100 ℃, then stirring the mixture at a low speed to 40 ℃, and then mixing the mixture by an open mill at 120 ℃ and die-pressing the mixture to obtain a semi-finished plate;
2) irradiating the semi-finished plate obtained in the step 1) by a cobalt source to 80kGy, carrying out mould pressing foaming at 210 ℃ and 10MPa for 4min, cooling and shaping, thus obtaining the PVC structural foam finished product of the embodiment 3.
The detection proves that the compression strength of the finished product of the example 3 is 1.80MPa, the Martin heat-resistant temperature is 98.5 ℃, and the water absorption is 2.0%.
Example 4
The PVC structural foam of the embodiment comprises the following raw materials in parts by weight:
Figure BDA0002270827180000092
the preparation method comprises the following steps:
1) uniformly mixing epoxy resin E44, an SH-200 curing agent and epoxy curing agent maleic anhydride according to the weight parts of the raw materials, then uniformly mixing the mixture with PVC resin, sequentially adding other raw material components, stirring the mixture at a high speed to 100 ℃, then stirring the mixture at a low speed to 40 ℃, and then mixing the mixture by an open mill at 110 ℃ and die-pressing the mixture to obtain a semi-finished plate;
2) irradiating the semi-finished plate obtained in the step 1) to 40kGy by using a cobalt source, foaming for 20min by using hot air at 190 ℃, cooling and shaping to obtain the PVC structural foam finished product of the example 4.
The detection proves that the compression strength of the finished product of the example 4 is 1.75MPa, the Martin heat-resisting temperature is 96.2 ℃, and the water absorption is 1.8%.
Example 5
The PVC structural foam of the embodiment comprises the following raw materials in parts by weight:
Figure BDA0002270827180000093
Figure BDA0002270827180000101
the preparation method comprises the following steps:
1) uniformly mixing the epoxy resin E51 and the SH-201 curing agent according to the weight parts of the raw materials, then uniformly mixing the mixture with the PVC resin, sequentially adding other raw material components, stirring the mixture at a high speed to 110 ℃, then stirring the mixture at a low speed to 40 ℃, and then mixing and die-pressing the mixture by using an open mill at a temperature of 130 ℃ to obtain a semi-finished plate;
2) irradiating the semi-finished plate obtained in the step 1) by a cobalt source to 50kGy, foaming by hot air at 200 ℃ for 25min, cooling and shaping to obtain the PVC structural foam finished product of the example 5.
The detection proves that the compression strength of the finished product of the example 5 is 1.53MPa, the Martin heat-resisting temperature is 95.2 ℃, and the water absorption is 1.7%.
Example 6
The PVC structural foam of the embodiment comprises the following raw materials in parts by weight:
Figure BDA0002270827180000102
the preparation method comprises the following steps:
1) uniformly mixing epoxy resin E44, an SH-200 curing agent and an epoxy curing agent phthalic anhydride according to the weight parts of the raw materials, then uniformly mixing the mixture with PVC resin, sequentially adding other raw material components, stirring the mixture at a high speed to 80 ℃, then stirring the mixture at a low speed to 40 ℃, and then mixing the mixture by an open mill at 120 ℃, and performing die pressing to obtain semi-finished plates;
2) irradiating the semi-finished plate obtained in the step 1) by using a cobalt source for 20kGy, foaming the semi-finished plate by hot air at 180 ℃ for 30min, and cooling and shaping to obtain the PVC structural foam finished product of the example 6.
The detection proves that the compression strength of the finished product of the example 6 is 1.69MPa, the Martin heat-resisting temperature is 94.3 ℃, and the water absorption is 1.2%.
Example 7
The PVC structural foam of the embodiment comprises the following raw materials in parts by weight:
Figure BDA0002270827180000111
the preparation method comprises the following steps:
1) uniformly mixing the epoxy resin SH-E50 with the epoxy value of 0.12, the epoxy curing agent dicyandiamide and phthalic anhydride according to the weight parts of the raw materials, uniformly mixing the mixture with PVC resin, sequentially adding other raw material components, stirring the mixture at a high speed to 100 ℃, then stirring the mixture at a low speed to 40 ℃, and then mixing, press-forming and cooling the mixture by using an open mill at 150 ℃ to obtain a semi-finished plate;
2) irradiating the semi-finished plate obtained in the step 1) by a cobalt source to 60kGy, foaming by hot air at 175 ℃ for 30min, cooling and shaping to obtain the PVC structural foam finished product of the example 7.
The detection proves that the compression strength of the finished product of the example 7 is 1.32MPa, the Martin heat-resisting temperature is 92.8 ℃, and the water absorption is 1.5%.
The above embodiments are preferred embodiments of the present invention, and all similar processes and equivalent variations to those of the present invention should fall within the scope of the present invention.

Claims (10)

1. The PVC structural foam is characterized by comprising the following raw material components in parts by weight: 100 parts of PVC resin, 5-80 parts of epoxy resin, 0.4-24 parts of epoxy curing agent, 5-20 parts of foaming agent, 3-20 parts of sensitizer, 1-8 parts of stabilizer and 5-15 parts of processing aid.
2. A PVC structural foam according to claim 1, characterized in that: the material comprises the following raw materials in parts by weight: 100 parts of PVC resin, 10-80 parts of epoxy resin, 0.8-24 parts of epoxy curing agent, 5-20 parts of foaming agent, 3-20 parts of sensitizer, 1-8 parts of stabilizer and 5-15 parts of processing aid.
3. A PVC structural foam according to claim 1 or 2, characterized in that: the epoxy value of the epoxy resin is 0.05-0.51 mol/100 g.
4. A PVC structural foam according to claim 1 or 2, characterized in that: the epoxy curing agent is at least one of dicyandiamide, maleic anhydride, phthalic anhydride, SH-201 curing agent and SH-200 curing agent.
5. A PVC structural foam according to claim 1 or 2, characterized in that: the foaming agent is at least one selected from azodicarbonamide, trihydrazino-s-triazine, N-nitroguanidine, p-methylsulfonylurea and phenyltetrazole.
6. A PVC structural foam according to claim 1 or 2, characterized in that: the sensitizer is at least one selected from the group consisting of trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, divinylbenzene, N '-4, 4' -diphenylmethane bismaleimide and triallyl isocyanate.
7. A PVC structural foam according to claim 1 or 2, characterized in that: the coating also comprises 0-10 parts of plasticizer, 0-2 parts of activating agent, 0-5 parts of lubricant and 0-20 parts of inorganic filler according to the parts by weight of the raw materials.
8. PVC structural foam according to claim 7, characterized in that: the activating agent is at least one of zinc stearate, calcium stearate, zinc oxide and urea.
9. A process for the preparation of PVC structural foam according to any of claims 1 to 8, characterized in that it comprises the following process steps:
1) uniformly mixing epoxy resin and an epoxy curing agent according to the weight parts of the raw materials, uniformly mixing the mixture with PVC resin, sequentially adding the raw material components except the epoxy resin and the epoxy curing agent, stirring the mixture at a high speed to 80-110 ℃, then stirring the mixture at a low speed to 40 ℃, and then mixing, press-forming and cooling the mixture to obtain a semi-finished plate;
2) carrying out irradiation crosslinking on the semi-finished plate obtained in the step 1) and then carrying out foaming treatment to obtain a finished product.
10. A process for the preparation of PVC structural foam according to claim 9, characterized in that: in the step 2), the irradiation crosslinking foaming treatment is to perform cobalt source or electron beam irradiation with irradiation dose of 4-80 kGy, and then foam in a mould pressing or hot air mode, wherein the foaming temperature is controlled to be 175-210 ℃, and the treatment time is 4-30 min.
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