CN106633467B - A method of preparing hard sandwich crosslinked PVC foamed material - Google Patents
A method of preparing hard sandwich crosslinked PVC foamed material Download PDFInfo
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- CN106633467B CN106633467B CN201510741657.8A CN201510741657A CN106633467B CN 106633467 B CN106633467 B CN 106633467B CN 201510741657 A CN201510741657 A CN 201510741657A CN 106633467 B CN106633467 B CN 106633467B
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- foamed material
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- crosslinked pvc
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- preparing hard
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- 239000000463 material Substances 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 28
- 239000004088 foaming agent Substances 0.000 claims abstract description 32
- 239000002608 ionic liquid Substances 0.000 claims abstract description 26
- 239000002994 raw material Substances 0.000 claims abstract description 19
- 239000003381 stabilizer Substances 0.000 claims abstract description 19
- 239000004094 surface-active agent Substances 0.000 claims abstract description 18
- 150000008065 acid anhydrides Chemical class 0.000 claims abstract description 16
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims abstract description 13
- -1 weigh dilute Corvic Substances 0.000 claims abstract description 12
- 238000005187 foaming Methods 0.000 claims abstract description 10
- 238000004132 cross linking Methods 0.000 claims abstract description 7
- 238000000643 oven drying Methods 0.000 claims abstract description 7
- 239000003999 initiator Substances 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims description 23
- 239000012948 isocyanate Substances 0.000 claims description 18
- 238000009835 boiling Methods 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 13
- 150000002513 isocyanates Chemical class 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 239000002131 composite material Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 7
- MUTGBJKUEZFXGO-OLQVQODUSA-N (3as,7ar)-3a,4,5,6,7,7a-hexahydro-2-benzofuran-1,3-dione Chemical compound C1CCC[C@@H]2C(=O)OC(=O)[C@@H]21 MUTGBJKUEZFXGO-OLQVQODUSA-N 0.000 claims description 6
- 239000004604 Blowing Agent Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 229920002732 Polyanhydride Polymers 0.000 claims description 5
- 235000021388 linseed oil Nutrition 0.000 claims description 5
- 239000000944 linseed oil Substances 0.000 claims description 5
- 239000000395 magnesium oxide Substances 0.000 claims description 5
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 4
- 239000006096 absorbing agent Substances 0.000 claims description 4
- 239000003063 flame retardant Substances 0.000 claims description 4
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 4
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 4
- 239000003921 oil Substances 0.000 claims description 4
- 235000019198 oils Nutrition 0.000 claims description 4
- 238000012856 packing Methods 0.000 claims description 4
- 239000000049 pigment Substances 0.000 claims description 4
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 3
- 244000068988 Glycine max Species 0.000 claims description 3
- 235000010469 Glycine max Nutrition 0.000 claims description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 2
- QYZFTMMPKCOTAN-UHFFFAOYSA-N n-[2-(2-hydroxyethylamino)ethyl]-2-[[1-[2-(2-hydroxyethylamino)ethylamino]-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCNCCO QYZFTMMPKCOTAN-UHFFFAOYSA-N 0.000 claims description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 claims 1
- 230000006641 stabilisation Effects 0.000 claims 1
- 238000011105 stabilization Methods 0.000 claims 1
- 239000004709 Chlorinated polyethylene Substances 0.000 abstract description 11
- 239000006261 foam material Substances 0.000 abstract description 6
- 229920000915 polyvinyl chloride Polymers 0.000 description 36
- 239000004800 polyvinyl chloride Substances 0.000 description 36
- 239000006260 foam Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- 230000005587 bubbling Effects 0.000 description 3
- 238000006735 epoxidation reaction Methods 0.000 description 3
- 239000004519 grease Substances 0.000 description 3
- 235000012245 magnesium oxide Nutrition 0.000 description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 3
- 239000011976 maleic acid Substances 0.000 description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- DGTNSSLYPYDJGL-UHFFFAOYSA-N phenyl isocyanate Chemical compound O=C=NC1=CC=CC=C1 DGTNSSLYPYDJGL-UHFFFAOYSA-N 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000004616 structural foam Substances 0.000 description 2
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 1
- 206010000269 abscess Diseases 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 1
- XOZUGNYVDXMRKW-AATRIKPKSA-N azodicarbonamide Chemical compound NC(=O)\N=N\C(N)=O XOZUGNYVDXMRKW-AATRIKPKSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000013877 carbamide Nutrition 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000013012 foaming technology Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
Abstract
The present invention relates to a kind of methods for preparing hard sandwich crosslinked PVC foamed material, weigh dilute Corvic, chlorinated polyethylene, isocyanates, ionic liquid surfactant, foaming agent, acid anhydrides, stabilizer be raw material, and using azodiisobutyronitrile as initiator, it is uniformly mixed in above-mentioned each component investment kneader, then by plasticizing forming, blank demoulding, vapor foaming and crosslinking, oven drying, it is prepared hard sandwich crosslinked PVC foamed material.Compared with prior art, the present invention makes the comprehensive performance of PVC foam material be greatly improved.
Description
Technical field
The present invention relates to a kind of preparation methods of foamed material, prepare hard sandwich crosslinked PVC hair more particularly, to a kind of
The method of foam material.
Background technique
Hard PVC foaming product has lot of advantages, and abscess fine and even, mechanical mechanics property is excellent.Cross-linked rigid
PVC foam is widely used in the application of the core filled composite materials such as wind energy, yacht, sports equipment, railway and space flight.But it is raw
There is also some problems for the technique of production PVC foam material, and such as because of the difference of production technology, PVC foam process be may result in
Degradation, the face of longer cured later time and the PVC foam toughness of products deficiency of foaming and mechanical mechanics property difference and product
Color problem etc..The stability problem of process about cross-linked rigid PVC foam material.Patent disclosure report, in formula
The epoxy component of 3%-15% is added as stabilizer and toughener, can alleviate the resolution problem in PVC process, but
Post-production extends curing time, in addition, can also further function as the effect of stable PVC foam by adding Ca Zn composite agent.
In addition the alkaline PVC and hexahydrophthalic anhydride using K value for 70 are also had been reported that, production efficiency, but because alkalinity can be improved
PVC affects the acidity of reaction environment, increases technique controlling difficulty, limits technological parameter.
Summary of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of comprehensive performances to obtain
The method for preparing hard sandwich crosslinked PVC foamed material being greatly improved.
The purpose of the present invention can be achieved through the following technical solutions:
A method of hard sandwich crosslinked PVC foamed material is prepared, using following steps:
(1) it stocks up: weighing dilute Corvic, chlorinated polyethylene, isocyanates, ionic liquid surfactant, foaming
Agent, acid anhydrides, stabilizer are raw material, and using azodiisobutyronitrile as initiator；
(2) stirring and heating in advance: it will uniformly be mixed in each component investment kneader in formula, control 20-40 DEG C of temperature, stir
Speed 500-1000r/min is mixed, is uniformly mixed raw material, while foaming agent being avoided to decompose, low boiling point solvent volatilization or each component
It does not chemically react；
(3) plasticizing forming: obtained mixed material is poured into mold, the pressurization of mold closure and heating, heating temperature
100-110 DEG C, polymerization reaction heat release occurs for mixture at this time, so that mold temperature is increased to 170-190 DEG C, mixed material is in the temperature
Spend lower plasticizing forming；For the excessively high and reaction of decomposing of preventing from heating up, cooling system is arranged in mold.
(4) mold temperature is down to 130-150 DEG C, then carries out blank demoulding；
(5) the prefoam blank after demoulding vapor foaming and crosslinking: is put into temperature water in 95 DEG C or more of hot water
4-6h is boiled, then in oven drying, that is, hard sandwich crosslinked PVC foamed material is prepared.
Corvic, chlorinated polyethylene be dilute in step (1), isocyanates, ionic liquid surfactant, foaming agent,
Acid anhydrides, stabilizer weight ratio be 100:1-10:30-120:0.05-2.5:3-12:1-30:3.
The isocyanates is the isocyanate compound with two or more multiple isocyanate functional groups.
Preferably, isocyanates includes but is not limited to 2,2 '-dimethyl -3,3 ', 5,5 '-triphenyl methane, four isocyanic acid
Ester, 2,4 toluene diisocyanate, 2,6- toluene di-isocyanate(TDI), hexamethylene diisocyanate, two isocyanide of diphenyl methane
Acid esters, 4,4' methylene bis (phenyl isocyanate) or isophorone diisocyanate.
The ionic liquid surfactant is following molecular structure:
Wherein, R1、R2、R3、R4For H, OH, SH or Me,
X=I, Br, Cl, PF6, BF4, SbF6,
The ionic liquid surfactant used is a kind of ionic liquid of long chain, and both ends have hydrophilic and oleophylic simultaneously
Compound, pass through premixing and stir the hard crosslinked PVC structural foam excellent come processability.Hydrophilic segment can effectively increase
Add the toughness of microvesicle, meanwhile, the part for having ionic liquid concurrently can more effectively dissolve low-boiling foaming agent, improve nucleation efficiencies.
In addition, by adding the dilute toughness to increase PVC foam of chlorinated polyethylene.
The foaming agent is low boiling point physical blowing agent or chemical foaming agent.
Preferably, low boiling point physical blowing agent is hexamethylene, 2,2 '-azobis isobutyronitrile of chemical foaming agent or azo two
One or both of carbamide.
Acid anhydrides described in the acid anhydrides is maleic acid bar, poly sebacic polyanhydride, one of hexahydrophthalic anhydride.
The stabilizer is epoxidation grease such as soya-bean oil, linseed oil, magnesia, in the metallic stabilizers such as Ca Zn composite agent
One kind.
One or more of pigment, ultraviolet absorbing agent, packing material or phosphorous flame-retardant material are also added in raw material.
The weight of Corvic accounts for the 40-60% of total weight in raw material.
Compared with prior art, the ionic liquid surfactant that the present invention uses for regulation system porous structure,
Shearing traction, the foamable polymer for improving mechanical performance have a direct impact.
Improve the toughness of microvesicle, frothing percentage, mechanical strength, by adding chlorination by addition ionic liquid surfactant
PVC improves the mechanical property of PVC composite material, due to the ionic liquid surface-active being dispersed on polyvinyl chloride resin, foaming agent
Bubbling efficiency greatly improves, so that PVC composite material foam shows excellent mechanical strength, that is, uses a small amount of foaming agent,
Higher bubbling efficiency can be still readily available.By introducing the dilute high tenacity having of chlorinated polyethylene in itself and excellent mechanical property
Can, finally make the comprehensive performance of PVC foam material be greatly improved.
For the present invention in addition to using crosslinked foaming technology, most distinct characteristic is to have used ionic liquid formula, is not only helped
In improvement cell density, while having the function of stable bubble hole.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.
A method of hard sandwich crosslinked PVC foamed material is prepared, using following steps:
(1) it stocks up: weighing dilute Corvic, chlorinated polyethylene, isocyanates, ionic liquid surfactant, foaming
Agent, acid anhydrides, stabilizer are raw material, and weight ratio is that weight ratio is 100:1-10:30-120:0.05-2.5:3-12:1-30:3,
And using azodiisobutyronitrile as initiator, wherein isocyanates is with two or more multiple isocyanate functional groups
Isocyanate compound, for example, can use 2,2 '-dimethyl -3,3 ', 5,5 '-triphenyl methane tetraisocyanates, 2,4-
Toluene di-isocyanate(TDI), 2,6- toluene di-isocyanate(TDI), hexamethylene diisocyanate, methyl diphenylene diisocyanate, 4,
4'- di-2-ethylhexylphosphine oxide (phenyl isocyanate) or isophorone diisocyanate.
Ionic liquid surfactant is following molecular structure:
Wherein, R1、R2、R3、R4For H, OH, SH or Me,
X=I, Br, Cl, PF6, BF4, SbF6,
The ionic liquid surfactant used is a kind of ionic liquid of long chain, this is that the present invention is creative
One place, both ends have hydrophilic and oleophylic compound simultaneously, are handed over by premixing stirring come the excellent hard of processability
Join PVC structural foam.Hydrophilic segment can effectively increase the toughness of microvesicle, meanwhile, the part for having ionic liquid concurrently can be more effective
Low-boiling foaming agent is dissolved, nucleation efficiencies are improved.
The dilute toughness that can increase PVC foam of the chlorinated polyethylene of addition, chlorination PVC improve the mechanics of PVC composite material
Performance, due to the ionic liquid surface-active being dispersed on polyvinyl chloride resin, the bubbling efficiency of foaming agent is greatly improved, so that PVC is multiple
Condensation material foam shows excellent mechanical strength, that is, uses a small amount of foaming agent, can still be readily available higher foaming effect
Rate, in addition, the dilute high tenacity having of chlorinated polyethylene in itself and excellent mechanical property, finally make the synthesis of PVC foam material
Performance is greatly improved, this is second innovative point of the invention.
Foaming agent is low boiling point physical blowing agent or chemical foaming agent.Such as low boiling point physical blowing agent is hexamethylene, is changed
Learning foaming agent is one or both of 2,2 '-azobis isobutyronitriles or azodicarboamide.
Acid anhydrides is maleic acid bar, poly sebacic polyanhydride, one of hexahydrophthalic anhydride.Stabilizer is epoxidation grease such as soya-bean oil,
Linseed oil, magnesia, one of metallic stabilizers such as Ca Zn composite agent.
In addition to this, it can also be added in raw material in pigment, ultraviolet absorbing agent, packing material or phosphorous flame-retardant material
One or more, the weight of Corvic accounts for the 40-60% of total weight in above-mentioned raw materials；
(2) stirring and heating in advance: it will uniformly be mixed in each component investment kneader in formula, control 20-40 DEG C of temperature, stir
Speed 500-1000r/min is mixed, is uniformly mixed raw material, while foaming agent being avoided to decompose, low boiling point solvent volatilization or each component
It does not chemically react；
(3) plasticizing forming: obtained mixed material is poured into mold, the pressurization of mold closure and heating, heating temperature
100-110 DEG C, polymerization reaction heat release occurs for mixture at this time, so that mold temperature is increased to 170-190 DEG C, mixed material is in the temperature
Spend lower plasticizing forming；For the excessively high and reaction of decomposing of preventing from heating up, cooling system is arranged in mold.
(4) mold temperature is down to 130-150 DEG C, then carries out blank demoulding；
(5) the prefoam blank after demoulding vapor foaming and crosslinking: is put into temperature water in 95 DEG C or more of hot water
4-6h is boiled, then in oven drying, that is, hard sandwich crosslinked PVC foamed material is prepared.
Embodiment 1
A method of hard sandwich crosslinked PVC foamed material is prepared, using following steps:
(1) raw material is weighed by weight: 100 parts of Corvic, dilute 5 parts of chlorinated polyethylene, isocyanates (MDI) 80
Part, 2 parts of this ionic liquid surfactant, 10 parts of foaming agent, 10 parts of acid anhydrides, 3 parts of stabilizer, and using AIBN as initiation
Agent, wherein the isocyanates used is 2,2 '-dimethyl -3,3 ', 5,5 '-triphenyl methane tetraisocyanates, ionic liquid body surface
Face activating agent is following molecular structure:
Wherein, R1、R2、R3、R4Respectively H, OH, SH, Me, X Br, foaming agent are hexamethylene, and acid anhydrides is maleic acid bar,
Poly sebacic polyanhydride, one of hexahydrophthalic anhydride, using maleic anhydride in the present embodiment.Stabilizer is epoxidation grease such as beans
Oil, linseed oil, magnesia, one of metallic stabilizers such as Ca Zn composite agent, using linseed oil in the present embodiment.
(2) stirring and heating in advance: each component is put into kneader and is uniformly mixed, controls 20 DEG C, mixing speed 1000r/
Min is uniformly mixed, while foaming agent being avoided to decompose, and low boiling point solvent volatilization or each component do not chemically react.
(3) plasticizing forming: mixture pours into mold, and the pressurization of mold closure and heating, mix at this time by 100 DEG C of heating temperature
It closes material and polymerization reaction heat release occurs, mold temperature is made to be increased to 180 DEG C or so, mixed material plasticizing forming at this temperature.For
It prevents from heating up excessively high and cooling system is arranged in reaction of decomposing, mold.
(4) at 130 DEG C, blank is demoulded for mold temperature control.
(5) vapor foaming and crosslinking.Prefoam blank after demoulding is put into temperature in 95 DEG C or more of hot water, water
It boils 4 hours.
(6) oven drying, is processed into product, and product mechanical property is seen attached list.
Embodiment 2
A method of hard sandwich crosslinked PVC foamed material is prepared, using following steps:
(1) stock up: by weight weighing for 100:1:30:0.05:3:1:3, Corvic, chlorinated polyethylene be dilute, isocyanide
Acid esters, ionic liquid surfactant, foaming agent, acid anhydrides, stabilizer are raw material, and using azodiisobutyronitrile as initiation
Agent, wherein the isocyanates used is 2,4- toluene di-isocyanate(TDI), and ionic liquid surfactant is following molecular structure:
Wherein, R1、R2、R3、R4It is H, X I, 2,2 '-azobis isobutyronitrile of foaming agent, acid anhydrides is poly sebacic polyanhydride,
Stabilizer is magnesia；
(2) stirring and heating in advance: it will uniformly be mixed in each component investment kneader in formula, control 30 DEG C of temperature, stirring
Speed 800r/min is uniformly mixed raw material, while foaming agent being avoided to decompose, and low boiling point solvent volatilization or each component are not changed
Learn reaction；
(3) plasticizing forming: obtained mixed material is poured into mold, the pressurization of mold closure and heating, heating temperature 100
DEG C, polymerization reaction heat release occurs for mixture at this time, so that mold temperature is increased to 170 DEG C, mixed material is plasticized at such a temperature
Type；For the excessively high and reaction of decomposing of preventing from heating up, cooling system is arranged in mold.
(4) mold temperature is down to 130 DEG C, then carries out blank demoulding；
(5) the prefoam blank after demoulding vapor foaming and crosslinking: is put into temperature water in 95 DEG C or more of hot water
4h is boiled, then in oven drying, that is, hard sandwich crosslinked PVC foamed material is prepared, product mechanical property is seen attached list.
Embodiment 3
A method of hard sandwich crosslinked PVC foamed material is prepared, using following steps:
(1) stock up: by weight for 100:10:120:2.5:12:30:3 weigh Corvic, chlorinated polyethylene it is dilute,
Isocyanates, ionic liquid surfactant, foaming agent, acid anhydrides, stabilizer are raw material, and using azodiisobutyronitrile as drawing
Send out agent, wherein the isocyanates used is 4,4'- di-2-ethylhexylphosphine oxide (phenyl isocyanate), and ionic liquid surfactant is following
Molecular structure:
Wherein, R1、R2、R3、R4It is H, X PF6, 2,2 '-azobis isobutyronitrile of foaming agent, acid anhydrides is hexahydrophthalic anhydride,
Stabilizer is Ca Zn composite agent；
(2) stirring and heating in advance: it will uniformly be mixed in each component investment kneader in formula, control 40 DEG C of temperature, stirring
Speed 500r/min is uniformly mixed raw material, while foaming agent being avoided to decompose, and low boiling point solvent volatilization or each component are not changed
Learn reaction；
(3) plasticizing forming: obtained mixed material is poured into mold, the pressurization of mold closure and heating, heating temperature 110
DEG C, polymerization reaction heat release occurs for mixture at this time, so that mold temperature is increased to 190 DEG C, mixed material is plasticized at such a temperature
Type；For the excessively high and reaction of decomposing of preventing from heating up, cooling system is arranged in mold.
(4) mold temperature is down to 150 DEG C, then carries out blank demoulding；
(5) the prefoam blank after demoulding vapor foaming and crosslinking: is put into temperature water in 95 DEG C or more of hot water
6h is boiled, then in oven drying, that is, hard sandwich crosslinked PVC foamed material is prepared.
Embodiment 4
A method of hard sandwich crosslinked PVC foamed material is prepared, it is substantially the same manner as Example 1, the difference is that,
It further include having pigment, ultraviolet absorbing agent in raw material in the present embodiment, the weight of Corvic accounts for the 40% of total weight.
Embodiment 5
A method of hard sandwich crosslinked PVC foamed material is prepared, it is substantially the same manner as Example 1, the difference is that,
It further include having packing material, phosphorous flame-retardant material in raw material in the present embodiment, the weight of Corvic accounts for total weight
60%.
1: two kind of different densities product (60,80kg/m of table3) mechanical property parameters
Claims (9)
1. a kind of method for preparing hard sandwich crosslinked PVC foamed material, which is characterized in that this method uses following steps:
(1) stock up: weigh Corvic, haloflex, isocyanates, ionic liquid surfactant, foaming agent,
Acid anhydrides, stabilizer are raw material, and using azodiisobutyronitrile as initiator；
(2) stirring and heating in advance: it will uniformly be mixed in each component investment kneader in formula, control 20-40 DEG C of temperature, stirring speed
500-1000r/min is spent, raw material is uniformly mixed；
(3) plasticizing forming: obtained mixed material is poured into mold, the pressurization of mold closure and heating, heating temperature 100-110
DEG C, polymerization reaction heat release occurs for mixture at this time, so that mold temperature is increased to 170-190 DEG C, mixed material is moulded at such a temperature
Chemical conversion type；
(4) mold temperature is down to 130-150 DEG C, then carries out blank demoulding；
(5) the prefoam blank after demoulding vapor foaming and crosslinking: is put into temperature boiling 4- in 95 DEG C or more of hot water
Hard sandwich crosslinked PVC foamed material is prepared then in oven drying in 6h；
The ionic liquid surfactant is following molecular structure:
Wherein, R1、R2、R3、R4For H, OH, SH or Me,
X=I, Br, Cl, PF6, BF4,SbF6,
2. a kind of method for preparing hard sandwich crosslinked PVC foamed material according to claim 1, which is characterized in that step
Suddenly Corvic, haloflex, isocyanates, ionic liquid surfactant, foaming agent, acid anhydrides, stabilization in (1)
The weight ratio of agent is 100:1-10:30-120:0.05-2.5:3-12:1-30:3.
3. a kind of method for preparing hard sandwich crosslinked PVC foamed material according to claim 1 or 2, which is characterized in that
The isocyanates is the isocyanate compound with two or more multiple isocyanate functional groups, including but is not limited to
In 2,2 '-dimethyl -3,3 ', 5,5 '-triphenyl methane tetraisocyanates, 2,4 toluene diisocyanate, 2,6- toluene two are different
Cyanate, hexamethylene diisocyanate, methyl diphenylene diisocyanate, 4,4' methylene bis (phenyl isocyanate) or different
Isophorone diisocyanate.
4. a kind of method for preparing hard sandwich crosslinked PVC foamed material according to claim 1 or 2, which is characterized in that
The foaming agent is low boiling point physical blowing agent or chemical foaming agent.
5. a kind of method for preparing hard sandwich crosslinked PVC foamed material according to claim 4, which is characterized in that institute
The low boiling point physical blowing agent stated is hexamethylene, and the chemical foaming agent is two phosphinylidyne of 2,2 '-azobis isobutyronitriles or azo
One or both of amine.
6. a kind of method for preparing hard sandwich crosslinked PVC foamed material according to claim 1 or 2, which is characterized in that
The acid anhydrides is one of maleic anhydride, poly sebacic polyanhydride or hexahydrophthalic anhydride, the stabilizer be soya-bean oil, linseed oil,
One of magnesia or Ca Zn composite metallic stabilizer.
7. a kind of method for preparing hard sandwich crosslinked PVC foamed material according to claim 1, which is characterized in that former
One or more of pigment, ultraviolet absorbing agent, packing material or phosphorous flame-retardant material are also added in material.
8. a kind of method for preparing hard sandwich crosslinked PVC foamed material according to claim 1 or claim 7, which is characterized in that
The weight of Corvic accounts for the 40-60% of total weight in raw material.
9. a kind of method for preparing hard sandwich crosslinked PVC foamed material according to claim 1, which is characterized in that step
Suddenly cooling system is additionally provided with outside mold in (3).
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102432813A (en) * | 2011-03-21 | 2012-05-02 | 常州凯诺深冷科技工程有限公司 | Method for preparing PIR (polyisocyanurate) material with ionic liquid catalyst |
| CN103509273A (en) * | 2012-06-29 | 2014-01-15 | 威海维赛新材料科技有限公司 | Modified rigid cross-linked polyvinyl chloride foam and preparation method thereof |
| CN104672706A (en) * | 2015-02-13 | 2015-06-03 | 中国科学院长春应用化学研究所 | Suspension PVC (Polyvinyl Chloride) resin-based foaming material and preparation method thereof |
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2015
- 2015-11-04 CN CN201510741657.8A patent/CN106633467B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102432813A (en) * | 2011-03-21 | 2012-05-02 | 常州凯诺深冷科技工程有限公司 | Method for preparing PIR (polyisocyanurate) material with ionic liquid catalyst |
| CN103509273A (en) * | 2012-06-29 | 2014-01-15 | 威海维赛新材料科技有限公司 | Modified rigid cross-linked polyvinyl chloride foam and preparation method thereof |
| CN104672706A (en) * | 2015-02-13 | 2015-06-03 | 中国科学院长春应用化学研究所 | Suspension PVC (Polyvinyl Chloride) resin-based foaming material and preparation method thereof |
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