CN101580573B - Improved crosslinked polyvinyl chloride structural foam and preparation method thereof - Google Patents

Improved crosslinked polyvinyl chloride structural foam and preparation method thereof Download PDF

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CN101580573B
CN101580573B CN200910033041XA CN200910033041A CN101580573B CN 101580573 B CN101580573 B CN 101580573B CN 200910033041X A CN200910033041X A CN 200910033041XA CN 200910033041 A CN200910033041 A CN 200910033041A CN 101580573 B CN101580573 B CN 101580573B
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polyvinyl chloride
crosslinked polyvinyl
structural foam
chloride structural
preparation
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CN101580573A (en
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朱文强
贲进
王健
吴海宙
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Changzhou Tiansheng New Materials Group Co ltd
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CHANGZHOU TIANSHENG NEO-MATERIAL Co Ltd
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Abstract

The invention relates to improved crosslinked polyvinyl chloride structural foam and a preparation method thereof. The foam is prepared from the following materials in portion by weight: 100 portions of polyvinyl chloride resin, 30 to 120 portions of isocyanate, 0.05 to 10 portions of epoxy components, 1 to 12 portions of foaming agent, 0.5 to 10 portions of triazine compound, and 1 to 30 portionsof acid anhydride. The preparation method thereof comprises the following steps: (1) mixing the raw materials evenly to obtain a pasty mixture; (2) pouring the pasty mixture obtained in step (1) into a die, and fully decomposing the foaming agent to obtain a semi-foaming die pressing block; (3) cooling the semi-foaming die pressing block to room temperature; (4) placing the semi-foaming die press ing block obtained in step (3) into hot bath or steam to carry out swelling; and (5) cooling a swelled semi-finished product obtained in step (4) to room temperature, and then adopting hot water sprayor curing post treatment in the steam to fully react the isocyanate so as to obtain cured block or plate crosslinked polyvinyl chloride structural foam. The foam has fine and even holes, and has good mechanical property and temperature resistance.

Description

A kind of improved crosslinked polyvinyl chloride structural foam and preparation method thereof
Technical field
The present invention relates to a kind of abscess fine and even, improved crosslinked polyvinyl chloride structural foam (cross-linked PVC structural foam) that mechanical mechanics property is good and preparation method thereof.
Background technology
Crosslinked rigid polyvinyl chloride foam has good static state and dynamic compression intensity, shock strength, rigidity, dimensional stability and higher resistance to fracture, is widely used in the composite component in the sandwiches application such as wind energy, yacht, sports equipment, railway locomotive and aerospace.
Patent WO 2005/092958 discloses a kind of initial feed prescription and preparation method who prepares the cross-linked polrvinyl chloride rigid foam; The epoxy component that has 3%-15% in its prescription is as stablizer and toughner; The interpolation of too much epoxy component has prolonged set time.It is trickle that patent WO 2007/141647 discloses a kind of improved abscess; The initial feed prescription and the preparation method of the rigid polyvinyl chloride foams of superior; Adopting specific raw material in its prescription, is 70 alkalescence (pH=10) SE and (methyl) HHPA like the K value, has shortened the process time; Improved production efficiency, resulting product has improved mechanical property within the specific limits.But the specific PVC RESINS and the selection of acid anhydrides, the while has also been reduced the acidity of reaction environment, has increased technique controlling difficulty, has limited the span of control of processing parameter (temperature, time).
Summary of the invention
For solving the problem that above-mentioned prior art exists, the present invention proposes a kind of improved crosslinked polyvinyl chloride structural foam of the excellent performance for preparing with the original mixture that contains triaizine compounds, specifically be prepared from by ratio of weight and the number of copies following material:
100 parts of PVC RESINSs, isocyanic ester 30-120 part, epoxy component 0.05-10 part, whipping agent 1-12 part, triaizine compounds 0.5-10 part, acid anhydrides 1-30 part.
The preferred ratio of weight and number of above-mentioned materials is:
100 parts of PVC RESINSs, isocyanic ester 45-100 part, epoxy component 0.05-2.5 part, whipping agent 3-12 part, triaizine compounds 1.5-8 part, acid anhydrides 10-25 part.
The weight of above-mentioned PVC RESINS accounts for the 35%-75% of original mixture weight, preferred 40%-60%, more preferably 44%-56%.
Described isocyanic ester is the isocyanate compound with two, three or more a plurality of functional groups.Said isocyanate component preferably has one of following general formula:
Q(NCO) i，
Wherein i is 2 or greater than 2 integer, Q is the organic free radical of i valency, can be to replace or unsubstituted alkyl (being alkylidene group or arylidene), also can be the group with following structural formula:
Q 1-Z-Q 1, Q wherein 1Be alkylene hydrocarbon or arylidene, Z is-O--O-Q 1-S-,-O-Q 1-,-CO-,-S-,-S-Q 1-S-,-SO-perhaps-SO 2-.Such isocyanate compound comprises: hexamethylene diisocyanate, 1 for example; 8-is diisocyanate based-and p-methane, diphenylmethanediisocyanate, cyclohexyl diisocyanate, phenylene diisocyanate, tolylene diisocyanate (comprises 2; 4-tolylene diisocyanate, 2; 6-tolylene diisocyanate and rough tolylene diisocyanate), diphenylmethanediisocyanate, chlorinated benzene vulcabond, ditan-4; 4 '-vulcabond (being also referred to as 4,4 '-diphenylmethanediisocyanate), naphthalene-1, the mixture of one or more arbitrary proportions in the compounds such as 5-vulcabond.
Q also can represent the polyurethane-base of i valency, in this case, and Q (NCO) iIt promptly is the compsn that is commonly referred to prepolymer.
The used isocyanic ester of the present invention can also be: the dimer of isocyanic ester and vulcabond and tripolymer and polymeric vulcabond for example, have following general formula:
[Q”(NCO) i] j
Wherein, i is 1 or greater than 1 integer, j be 2 or greater than 2 integer, Q " be multifunctional organic group.Such isocyanate compound preferred polymeric vulcabond and isocyanate trimerization body, described polymeric vulcabond comprise, for example polymethylene multi-phenenyl isocyanate etc.Described isocyanate trimerization body can be any isocyanate trimerization body in the prior art, preferred following homopolymerization tripolymer, tercopolyureas aggressiveness or homopolymerization tripolymer and the trimerical mixture of copolymerization.Homopolymerization isocyanate trimerization body comprises: hexamethylene diisocyanate homopolymerization tripolymer, tolylene diisocyanate homopolymerization tripolymer, different Buddhist diketone vulcabond homopolymerization tripolymer, 4; 4 '-ditan-vulcabond homopolymerization tripolymer, diphenylmethanediisocyanate homopolymerization tripolymer, 4; The mixture of one or more in 4-dicyclohexyl methane diisocyanate homopolymerization tripolymer, fourth vulcabond homopolymerization tripolymer, hot vulcabond homopolymerization tripolymer, the last of the ten Heavenly stems homopolymerization tripolymer such as vulcabond homopolymerization tripolymer and naphthalene diisocyanate homopolymerization tripolymer, the mixture of one or more arbitrary proportions in the homopolymerization tripolymers such as preferred hexamethylene diisocyanate homopolymerization tripolymer, tolylene diisocyanate homopolymerization tripolymer, 4-dicyclohexyl methane diisocyanate homopolymerization tripolymer, different Buddhist diketone vulcabond homopolymerization tripolymer and diphenylmethanediisocyanate homopolymerization tripolymer; Copolymerization isocyanate trimerization body comprises: oneself two isocyanic acids, tolylene diisocyanate, different Buddhist diketone vulcabond, 4; 4 '-ditan-vulcabond, diphenylmethanediisocyanate and 4, the tercopolyureas aggressiveness between the 4-dicyclohexyl methane diisocyanate.Wherein, described polyisocyanate trimer is hexamethylene diisocyanate homopolymerization tripolymer more preferably, and its structural formula is following:
Figure G200910033041XD00031
Q " also can be the compound with following general formula:
L(NCO) i
Wherein, i is 1 or greater than 1 integer, L is simple function or multifunctional atom or group.The compound of the type comprises: for example ethylphosphonic acid vulcabond, C 2H 5P (O) (NCO) 2, phenyl-phosphonic acid vulcabond, C 6H 5P (O) (NCO) 2, contain the compound of trivalent silicon cyanate group, the mixture of one or more arbitrary proportions in the compounds such as isocyanic ester that form by sulphonamide, cyanic acid and thiocyanic acid.
The above-mentioned isocyanic ester of mentioning can use separately, also can use more than one mixture.Usually preferred isocyanic ester is fragrant POLYMETHYLENE POLYPHENYLISOCYANATE, because their reactive behavior is bigger.Preferred isocyanic ester is a ditan-4; 4 '-vulcabond, poly methylene poly phenyl poly isocyanate, liquefaction ditan-4, the mixture of one or more arbitrary proportions in 4 '-vulcabond and the hexamethylene diisocyanate homopolymerization tripolymer compound.
Above-mentioned organic acid anhydride can be the organic acid anhydride that is the basis with one or more basic carboxylic acids; For example Tetra hydro Phthalic anhydride, maleic anhydride, Succinic anhydried (succinyl oxide), Citric anhydride, itaconic anhydride, trimellitic acid 1,2-anhydride, HHPA, methyl hexahydrophthalic anhydride, hexanaphthene-1,2-dicarboxylic anhydride, dodecenylsuccinic anhydride and pyromellitic acid anhydride etc.The above-mentioned acid anhydrides of mentioning can use separately, also can use the mixture of more than one arbitrary proportions.
Above-mentioned whipping agent can be an azo class chemical foaming agent, for example Diisopropyl azodicarboxylate, Cellmic C 121 and their mixture.Preferred Diisopropyl azodicarboxylate and Cellmic C 121 are by 1.05: 1-8: the mixture of 1 weight ratio preparation.
Above-mentioned epoxy component can be epoxidized vegetable oil or epoxy animal oil (for example epoxy soybean oil, epoxy Yatall MA and epoxy Semen Lini wet goods), epoxy resin, epoxidized triglyceride and oxirane etc.The above-mentioned epoxy component of mentioning can be used separately, also can use the mixture of more than one arbitrary proportions.The above-mentioned epoxy component preferably vegetable oil of mentioning belongs to renewable resources, more preferably epoxy soybean oil.
Above-mentioned triaizine compounds can be amino substituted triazine ring compound, for example contains amino 1,3,5-triazines compounds, contains 1 of amino; 2,3-compound in triazine class (5-position, 4,5-position, 4,5; Go up by amino substituted 1,2 6-positions etc., 3-triazine, 4-amino-benzene-1,2; 3-triazine etc.), contain 1,2 of amino, 4-compound in triazine class (3-position, 5-position, 3; Go up by amino substituted 1,2 5-positions etc., 4-triazine etc.) etc. the mixture of one or more arbitrary proportions in the compound in triazine class of various amino.Preferably contain amino 1,3,5-triazines compounds; Amino is that (particularly carbon atom) replaces on the suitable atom of triazine ring; Amino number has no particular limits, and can be 1-3, preferred 2-3; For example: trimeric cyanamide compounds [trimeric cyanamide, the substituted melamine (C of 2-methyl melamine and so on for example 1To C 4Alkyl melamine, amidino groups trimeric cyanamide and benzoguanamine etc.)], trimeric cyanamide condenses (for example melam, melem and mellon etc.), the cocondensation resin of trimeric cyanamide (for example melamine formaldehyde resin, phenol-melamine resin, benzo guanamine-melamine resin and aromatic series polyamine-melamine resin etc.); Tricyanic acid amides (for example trimeric cyanamide diamide, trimeric cyanamide monoamide etc. and binary melamine compound etc.), guanamines compounds [guanamines, alkyl substituted guanidines amine (for example methylguanidine amine etc.); Acyl group guanamines (for example acetylguanamine etc.), aromatic series guanamines (for example benzo guanamine, phenylacetyl guanamines and phthalyl guanamines etc.), alicyclic ring guanamines (for example hexanaphthene guanamines etc.); Aliphatics guanamines (for example W-37 amine and oneself two guanamines etc.); CTU-guanamines (for example 2,4,8; 10-four oxygen spiral shells (5; 5) propylene guanamines etc. undecane-3,9 pair (2-ethyl guanamines) etc.) ,] etc.The above-mentioned triaizine compounds of mentioning can use separately or more than one arbitrary proportions mix use.Preferred triaizine compounds comprises trimeric cyanamide, benzoguanamine, phthalyl guanamines, melam and methylguanidine amine.
The effect of nucleator is played in the adding of triaizine compounds on the one hand, can be used as the response type monomer on the other hand, has reduced the acidity of reaction environment, has increased the network structure of reaction, has improved the temperature tolerance of material.In addition, the triaizine compounds of adding has fire-retardant effect, and therefore, the present invention does not need to add extra fire retardant again.
As required, also can add in this area various additives commonly used among the present invention, tensio-active agent for example, pigment or dyestuff, pigment dispersing agent, packing material, UV light absorber, nucleator etc.
As required, also can add all kinds of SOLVENTS commonly used in this area among the present invention, for example halohydrocarbon, toluene, acetone, hexane etc.
Preparing method of the present invention comprises the steps:
(1) in mixing machine, mixes the solid-liquid raw material,, obtain pasty mixture until mixing;
(2) pasty mixture that step (1) is obtained is poured in the mould, under certain temperature and pressure, makes whipping agent decompose fully, obtains half foaming shape mold pressing piece;
(3) cooling is partly foamed shape mold pressing thing to room temperature;
(4) refrigerative that step (3) the is obtained shape mold pressing thing that partly foams places hot water bath or steam, expands up to final density;
The work in-process cool to room temperature of the expansion that (5) step (4) is obtained adopts hot water spray then or in steam, solidifies aftertreatment, reacts remaining isocyanic ester, the block or tabular crosslinked polyvinyl chloride structural foam that obtains being cured.
In the above-mentioned steps (2), at a certain temperature, whipping agent generation decomposition reaction, SE generation gel reaction.Under certain pressure, chemical foaming agent decomposes the gas dissolvings such as nitrogen of generation in gel polyvinyl chloride, forms tiny complex.Gel reaction carries out under the gelling temp of SE, and TR is 150-200 ℃, preferred 160-180 ℃; Pressure range is 10-30MPa, preferred 12-20MPa.
In the above-mentioned steps (2), described mould can be aluminum or steel die.
In the above-mentioned steps (4), because the existence of moisture, the shape mold pressing thing that partly foams expands and crosslinking reaction simultaneously.Main chemical reaction is the reaction between a series of mixtures such as water, isocyanic ester, acid anhydrides and triaizine compounds.The reaction that most probable takes place is that isocyanic ester and water reaction form amine and atmospheric carbon dioxide, and its reaction formula is following:
RNCO+H 2O→RNH 2+C O2
In the above-mentioned steps (4), expansion temperature is 80-100 ℃, preferred 85-100 ℃.
In the above-mentioned steps (5), the post-processing temperature of water spray or steam is 40-70 ℃, preferred 45-65 ℃.
The present invention has following advantage:
1, ME control is simple, and the parameter operating restraint is wide, shortens the process time, has improved product percent of pass, and has not had the problem of environmental protection aspect;
2, the three-dimensional arrangement that contains triaizine compounds, product have certain three-dimensional net structure, have improved the temperature tolerance of material, and product can be processed under up to 90 ℃ temperature, and size deformation is little, and successive process operation TR-200 is ℃ to 75 ℃;
3, abscess fine and even (the about 300 μ m in aperture), mechanical mechanics properties such as compressive strength, tensile modulus and shear strain are good.
Embodiment
Through embodiment the present invention is specifically described below, it is important to point out that following examples can only be used for the present invention is further specified, can not be interpreted as restriction protection domain of the present invention.
Embodiment 1
Comprise the SE double centner in the mixture, liquefaction ditan-4,66 kilograms of 4 '-vulcabond; 12.6 kilograms of poly methylene poly phenyl poly isocyanates, 1.6 kilograms of epoxy soybean oils, 7.0 kilograms of Diisopropyl azodicarboxylates; 1.8 kilograms of Cellmic C 121s; 3.0 kilograms of trimeric cyanamides, 20.6 kilograms of methyl hexahydrophthalic anhydrides, 1.2 kilograms in tensio-active agent.In mixing machine, mix until evenly, obtain the pasty mixture of certain viscosity.
Product is poured in the steel die that thickness is 28mm, filled up mould.It is placed between 175 ℃ the press flat board heat, pressure is 14MPa.Mixture is cool to room temperature and taking-up under pressure, obtains the refrigerative shape mold pressing thing that partly foams.
Then, the shape mold pressing thing that will partly foam is positioned in the steam baking oven and expanded 6 hours, and vapor temperature is 93 ℃ ± 2 ℃.After the cooling, in 65 ℃ steam baking oven, solidify aftertreatment 5 days, isocyanic ester is reacted fully, obtain the rigid foam product thus, density is 62kg/m 3Its mechanical mechanics property data are as shown in table 1)
Embodiment 2
Comprise the SE double centner in the mixture, liquefaction ditan-4,88 kilograms of 4 '-vulcabond; 8.6 kilograms of poly methylene poly phenyl poly isocyanates, 1.0 kilograms of epoxy soybean oils, 8.2 kilograms of Diisopropyl azodicarboxylates; 1.1 kilograms of Cellmic C 121s; 5 kilograms of trimeric cyanamides, 10 kilograms of methyl hexahydrophthalic anhydrides, 2.1 kilograms in tensio-active agent.In mixing machine, mix until evenly, obtain the pasty mixture of certain viscosity.
Product is poured in the steel die that thickness is 28mm, filled up mould.It is placed between 175 ℃ the press flat board heat, pressure is 15MPa.Mixture is cool to room temperature and taking-up under pressure, obtains the refrigerative shape mold pressing thing that partly foams.
Then, the shape mold pressing thing that will partly foam is positioned in the steam baking oven and expanded 6 hours, and vapor temperature is 96 ℃ ± 2 ℃.After the cooling, solidify aftertreatment 5 days with 65 ℃ hot water spray, isocyanic ester is reacted fully, obtain the rigid foam product thus, density is 70kg/m 3Its mechanical mechanics property data are as shown in table 1)
Embodiment 3
Comprise the SE double centner in the mixture; 30 kilograms of poly methylene poly phenyl poly isocyanates, 29 kilograms of liquefaction diphenylmethanediisocyanates, 1.5 kilograms of epoxy soybean oils; 6.6 kilograms of Diisopropyl azodicarboxylates; 1.5 kilograms of Cellmic C 121s, 3.0 kilograms of trimeric cyanamides, 19.4 kilograms of Tetra hydro Phthalic anhydrides.In mixing machine, mix until evenly, obtain the pasty mixture of certain viscosity.
Product is poured in the aluminium-making mould that thickness is 28mm, filled up mould.It is placed between 165 ℃ the press flat board heat, pressure is 12MPa.Mixture is cool to room temperature and taking-up under pressure, obtains the refrigerative shape mold pressing thing that partly foams.
Then, the shape mold pressing thing that will partly foam is positioned in the steam baking oven and expanded 4 hours, and vapor temperature is 97 ℃ ± 2 ℃.After the cooling, in 60 ℃ steam baking oven, solidify aftertreatment 9 days, isocyanic ester is reacted fully, obtain the rigid foam product thus, density is 61kg/m 3Its mechanical mechanics property data are as shown in table 1)
Embodiment 4
Comprise the SE double centner in the mixture, 45 kilograms of tolylene diisocyanates, 15 kilograms of diphenylmethanediisocyanates; 1 kilogram of epoxy Yatall MA, 6.2 kilograms of Diisopropyl azodicarboxylates, 1.8 kilograms of Cellmic C 121s; 3.8 kilograms of benzoguanamines, 21.5 kilograms of HHPAs.In mixing machine, mix until evenly, obtain the pasty mixture of certain viscosity.
Product is poured in the aluminium-making mould that thickness is 28mm, filled up mould.It is placed between 160 ℃ the press flat board heat, pressure is 14MPa.Mixture is cool to room temperature and taking-up under pressure, obtains the refrigerative shape mold pressing thing that partly foams.
Then, the shape mold pressing thing that will partly foam is positioned in the steam baking oven and expanded 6 hours, and vapor temperature is 92 ℃ ± 2 ℃.After the cooling, in 55 ℃ steam baking oven, solidify aftertreatment 10 days, isocyanic ester is reacted fully, obtain the rigid foam product thus, density is 68kg/m 3About.Its mechanical mechanics property data are as shown in table 1)
Embodiment 5
Comprise the SE double centner in the mixture, 11.5 kilograms of diphenylmethanediisocyanates, 45 kilograms of phenylene diisocyanates; 0.6 kilogram of isophorone diisocyanate homopolymerization tripolymer, 1 kilogram of epoxy soybean oil, 6.8 kilograms of Diisopropyl azodicarboxylates; 1.8 kilograms of Cellmic C 121s; 3.0 kilograms of benzoguanamines, 13 kilograms of maleic anhydrides, 7.8 kilograms of Citric anhydrides.In mixing machine, mix until evenly, obtain the pasty mixture of certain viscosity.
Product is poured in the aluminium-making mould that thickness is 28mm, filled up mould.It is placed between 175 ℃ the press flat board heat, pressure is 13MPa.Mixture is cool to room temperature and taking-up under pressure, obtains the refrigerative shape mold pressing thing that partly foams.
Then, the shape mold pressing thing that will partly foam is positioned in the hot water bath and expanded 6 hours, and the hot water bath temperature is 92 ℃ ± 2 ℃.After the cooling, in 65 ℃ steam baking oven, solidify aftertreatment 10 days, isocyanic ester is reacted fully, obtain the rigid foam product thus, density is 64kg/m 3About.Its mechanical mechanics property data are as shown in table 1)
Embodiment 6
Comprise the SE double centner in the mixture, 7.3 kilograms of chlorinated benzene vulcabond, 51.2 kilograms of hexamethylene diisocyanate homopolymerization tripolymers; 0.7 kilogram of epoxy Toenol 1140; 5.3 kilograms of Diisopropyl azodicarboxylates, 1.8 kilograms of Cellmic C 121s, 2.6 kilograms of phthalyl guanamines; 3.5 kilograms of Succinic anhydrieds, 14 kilograms of itaconic anhydrides.In mixing machine, mix until evenly, obtain the pasty mixture of certain viscosity.
Product is poured in the steel die that thickness is 28mm, filled up mould.It is placed between 165 ℃ the press flat board heat, pressure is 20MPa.Mixture is cool to room temperature and taking-up under pressure, obtains the refrigerative shape mold pressing thing that partly foams.
Then, the shape mold pressing thing that will partly foam is positioned in the hot water bath and expanded 4 hours, and the hot water bath temperature is 96 ℃ ± 2 ℃.After the cooling, in 45 ℃ steam baking oven, solidify aftertreatment 12 days, isocyanic ester is reacted fully, obtain the rigid foam product thus, density is 83kg/m 3About.Its mechanical mechanics property data are as shown in table 1)
Embodiment 7
Comprise the SE double centner in the mixture, 37 kilograms of diphenylmethanediisocyanates, 12 kilograms of phenyl-phosphonic acid vulcabond; 0.7 kilogram of epoxy soybean oil; 5.4 kilograms of Diisopropyl azodicarboxylates, 1.5 kilograms of Cellmic C 121s, 1.9 kilograms of melams; 9.8 kilograms of cyclohexane dicarboxylic acid acid anhydrides, 15 kilograms of Tetra hydro Phthalic anhydrides.In mixing machine, mix until evenly, obtain the pasty mixture of certain viscosity.
Product is poured in the aluminium-making mould that thickness is 28mm, filled up mould.It is placed between 170 ℃ the press flat board heat, pressure is 15MPa.Mixture is cool to room temperature and taking-up under pressure, obtains the refrigerative shape mold pressing thing that partly foams.
Then, the shape mold pressing thing that will partly foam is positioned in the hot water bath and expanded 4 hours, and the hot water bath temperature is 98 ℃ ± 2 ℃.After the cooling, in 50 ℃ steam baking oven, solidify aftertreatment 7 days, isocyanic ester is reacted fully, obtain the rigid foam product thus, density is 85kg/m 3About.Its mechanical mechanics property data are as shown in table 1)
Embodiment 8
Comprise the SE double centner in the mixture, 38 kilograms of tolylene diisocyanates, 9 kilograms of isophorone diisocyanates; 0.7 kilogram of epoxidized triglyceride, 3 kilograms of Diisopropyl azodicarboxylates, 1.8 kilograms of Cellmic C 121s; 0.8 kilogram of methylguanidine amine, 5 kilograms of phthalic anhydrides, 20 kilograms of pyromellitic acid anhydrides.In mixing machine, mix until evenly, obtain the pasty mixture of certain viscosity.
Product is poured in the steel die that thickness is 28mm, filled up mould.It is placed between 180 ℃ the press flat board heat, pressure is 17MPa.Mixture is cool to room temperature and taking-up under pressure, obtains the refrigerative shape mold pressing thing that partly foams.
Then, the shape mold pressing thing that will partly foam is positioned in the steam baking oven and expanded 5 hours, and vapor temperature is 98 ℃ ± 2 ℃.After the cooling, in 60 ℃ steam baking oven, solidify aftertreatment 5 days, isocyanic ester is reacted fully, obtain the rigid foam product thus, density is 76kg/m 3About.Its mechanical mechanics property data are as shown in table 1)
Comparative example (applicant's currently available products)
Comprise the SE double centner in the mixture, 25 kilograms of poly methylene poly phenyl poly isocyanates, 32 kilograms of tolylene diisocyanates; 2.5 kilograms of epoxy soybean oils; 10 kilograms of Diisopropyl azodicarboxylates, 2.0 kilograms of Cellmic C 121s, 35 kilograms of Tetra hydro Phthalic anhydrides; In mixing machine, mix until evenly, obtain the pasty mixture of certain viscosity.
Product is poured in the steel die that thickness is 28mm, filled up mould.It is placed between 175 ℃ the press flat board heat, pressure is 18MPa.Mixture is cool to room temperature and taking-up under pressure, obtains the refrigerative shape mold pressing thing that partly foams.
Then, the shape mold pressing thing that will partly foam is positioned in the steam baking oven and expanded 10 hours, and vapor temperature is 93 ℃ ± 2 ℃.After the cooling, in 65 ℃ steam baking oven, solidify aftertreatment 12 days, isocyanic ester is reacted fully, obtain the rigid foam product thus, density is 60kg/m 3Its mechanical mechanics property data are as shown in table 1)
The mechanical mechanics property data sheet of table 1 embodiment 1-8 and comparative example
Annotate: all values are the test value under+23 ℃.
About the product that the method in this patent is made, no matter be compression performance, tensile property still is that cutting performance is all taller than the product performance of like product or the preparation of employing related patent U.S. Patent No. method; Especially tensile modulus (having increased by 1 times) and shear strain have had significant raising (having increased nearly 1 times); Toughness has significantly improved, and mechanical stability and temperature tolerance have also improved, and adopts the product of this patent preparation; Can under up to 90 ℃ temperature, process, and size deformation is little.Successive process operation TR-200 is ℃ to 75 ℃.Therefore, the foamed products of preparation can be used for the core filled composite material of the application such as industry, transportation, boats and ships and wind power generation of severe environment.

Claims (21)

1. an improved crosslinked polyvinyl chloride structural foam is characterized in that being prepared from by ratio of weight and the number of copies following material: 100 parts of PVC RESINSs, isocyanic ester 30-120 part; Epoxy component 0.05-10 part; Whipping agent 1-12 part, triaizine compounds 0.5-10 part, acid anhydrides 1-30 part; Aforementioned described isocyanic ester is the isocyanate compound with two, three or more a plurality of functional groups.
2. crosslinked polyvinyl chloride structural foam according to claim 1 is characterized in that being prepared from by ratio of weight and the number of copies following material: 100 parts of PVC RESINSs, isocyanic ester 45-100 part; Epoxy component 0.05-2.5 part; Whipping agent 3-12 part, triaizine compounds 1.5-8 part, acid anhydrides 10-25 part.
3. crosslinked polyvinyl chloride structural foam according to claim 1 or claim 2 is characterized in that the weight of described PVC RESINS accounts for the 35%-75% of original mixture weight.
4. like the said crosslinked polyvinyl chloride structural foam of claim 3, it is characterized in that the weight of described PVC RESINS accounts for the 40%-60% of original mixture weight.
5. like the said crosslinked polyvinyl chloride structural foam of claim 4, it is characterized in that the weight of described PVC RESINS accounts for the 44%-56% of original mixture weight.
6. crosslinked polyvinyl chloride structural foam according to claim 1 is characterized in that described isocyanic ester is the isocyanate compound with one of following general formula:
1)Q(NCO) i
Wherein i is 2 or greater than 2 integer, Q is the organic free radical of i valency, can be to replace or unsubstituted alkyl is alkylidene group or arylidene, or have the group of following structural formula: Q 1-Z-Q 1, Q wherein 1Be alkylene hydrocarbon or arylidene, Z is-O--O-Q 1-S-,-O-Q 1-,-CO-,-S-,-S-Q 1-S-,-SO-perhaps-SO 2-, or the polyurethane-base of i valency;
2)[Q”(NCO) i] j
Wherein, i is 1 or greater than 1 integer, j be 2 or greater than 2 integer, Q " be multifunctional organic group.
7. like the said crosslinked polyvinyl chloride structural foam of claim 6; It is characterized in that described isocyanic ester is selected from ditan-4; 4 '-vulcabond, liquefaction ditan-4, the mixture of one or more arbitrary proportions in 4 '-vulcabond, poly methylene poly phenyl poly isocyanate or the hexamethylene diisocyanate homopolymerization tripolymer compound.
8. crosslinked polyvinyl chloride structural foam according to claim 1 or claim 2; It is characterized in that described acid anhydrides is selected from Tetra hydro Phthalic anhydride, maleic anhydride, Succinic anhydried, Citric anhydride, itaconic anhydride, trimellitic acid 1,2-anhydride, HHPA, methyl hexahydrophthalic anhydride, hexanaphthene-1, the mixture of one or more arbitrary proportions in 2-dicarboxylic anhydride, dodecenylsuccinic anhydride or the pyromellitic acid anhydride.
9. crosslinked polyvinyl chloride structural foam according to claim 1 or claim 2, it is characterized in that described whipping agent be Diisopropyl azodicarboxylate and Cellmic C 121 by 1.05: 1-8: the mixture of 1 weight ratio preparation.
10. crosslinked polyvinyl chloride structural foam according to claim 1 or claim 2 is characterized in that described epoxy component is epoxidized vegetable oil, epoxy animal oil, epoxy resin, the mixture of one or more arbitrary proportions in epoxidized triglyceride or the oxirane.
11. crosslinked polyvinyl chloride structural foam is characterized in that described triaizine compounds is amino substituted triazine ring compound according to claim 1 or claim 2.
12. like the said crosslinked polyvinyl chloride structural foam of claim 11; It is characterized in that described triaizine compounds is to contain amino 1,3,5-triazines compound, contain amino 1; 2; The 3-compound in triazine class or contain amino 1,2, the mixture of one or more arbitrary proportions in the 4-compound in triazine class.
13. the preparation method of any said crosslinked polyvinyl chloride structural foam of claim 1 to 12 is characterized in that comprising the steps:
(1) each raw materials mix is even, obtain pasty mixture;
(2) pasty mixture that step (1) is obtained is poured in the mould, and whipping agent is decomposed fully, obtains half foaming shape mold pressing piece;
(3) cooling is partly foamed shape mold pressing thing to room temperature;
(4) the shape mold pressing thing that partly foams that step (3) is obtained places hot water bath or steam to expand;
The work in-process cool to room temperature of the expansion that (5) step (4) is obtained adopts hot water spray then or in steam, solidifies aftertreatment, and isocyanic ester is reacted fully, the block or tabular crosslinked polyvinyl chloride structural foam that obtains being cured.
14., it is characterized in that the molding temperature in the step (2) is 150-200 ℃ like the preparation method of the said crosslinked polyvinyl chloride structural foam of claim 13.
15., it is characterized in that the molding temperature in the step (2) is 160-180 ℃ like the preparation method of the said crosslinked polyvinyl chloride structural foam of claim 14.
16., it is characterized in that the molding pressure in the step (2) is 10-30MPa like the preparation method of the said crosslinked polyvinyl chloride structural foam of claim 13.
17., it is characterized in that the molding pressure in the step (2) is 12-20MPa like the preparation method of the said crosslinked polyvinyl chloride structural foam of claim 16.
18., it is characterized in that the expansion temperature in the step (4) is 80-100 ℃ like the preparation method of the said crosslinked polyvinyl chloride structural foam of claim 13.
19., it is characterized in that the expansion temperature in the step (4) is 85-100 ℃ like the preparation method of the said crosslinked polyvinyl chloride structural foam of claim 18.
20., it is characterized in that the post-processing temperature in the step (5) is 40-70 ℃ like the preparation method of the said crosslinked polyvinyl chloride structural foam of claim 13.
21., it is characterized in that the post-processing temperature in the step (5) is 45-65 ℃ like the preparation method of the said crosslinked polyvinyl chloride structural foam of claim 20.
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CN102391434B (en) * 2011-08-23 2013-04-24 中国科学院长春应用化学研究所 Crosslinked polyvinyl chloride foam and preparation method thereof
CN103524948B (en) * 2013-10-25 2016-01-20 中国科学院长春应用化学研究所 A kind of polyvinyl chloride foam and preparation method thereof
CA2932723C (en) 2013-12-12 2022-08-23 Diab International Ab Apparatus and method for the production of expanded foam embryos
CN104672705B (en) * 2015-02-13 2018-02-13 中国科学院长春应用化学研究所 Crosslinked polyvinyl chloride foam and preparation method thereof
CN104672706B (en) * 2015-02-13 2017-08-11 中国科学院长春应用化学研究所 Foamed material based on suspension pvc resin and preparation method thereof
CN105440497A (en) * 2015-12-24 2016-03-30 刘家容 Antifoulingflame-retardant plastic floor and preparation method thereof
CN107603071B (en) * 2017-10-18 2019-09-17 清华大学 A kind of PVC foamed composite and preparation method thereof of resinous paint slag
CN109054233A (en) * 2018-07-12 2018-12-21 洛阳科博思新材料科技有限公司 A kind of micropore PVC foamed material and preparation method thereof
CN110002910A (en) * 2018-11-20 2019-07-12 河北农业大学 A kind of organic fertilizer flowerpot and preparation method thereof based on foamed polymer carrier
CN111004456B (en) * 2019-11-01 2022-06-24 石河子大学 Light-weight high-strength heat-resistant polyvinyl chloride foam material and preparation method thereof
CN110982189B (en) * 2019-11-13 2021-10-22 佛山佛塑科技集团股份有限公司 PVC structural foam and preparation method thereof

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