CN1301279C - Polyurethane hard foamed plastics and its preparing method - Google Patents
Polyurethane hard foamed plastics and its preparing method Download PDFInfo
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- CN1301279C CN1301279C CNB2003101121772A CN200310112177A CN1301279C CN 1301279 C CN1301279 C CN 1301279C CN B2003101121772 A CNB2003101121772 A CN B2003101121772A CN 200310112177 A CN200310112177 A CN 200310112177A CN 1301279 C CN1301279 C CN 1301279C
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- polyethers
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- combined polyether
- high pressure
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- 239000004033 plastic Substances 0.000 title claims abstract description 23
- 229920003023 plastic Polymers 0.000 title claims abstract description 23
- 239000004814 polyurethane Substances 0.000 title claims abstract description 12
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 10
- 238000000034 method Methods 0.000 title claims abstract description 6
- 229920000570 polyether Polymers 0.000 claims abstract description 75
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 32
- 238000005187 foaming Methods 0.000 claims abstract description 16
- 239000006260 foam Substances 0.000 claims abstract description 14
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 13
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 13
- 239000003381 stabilizer Substances 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 238000002347 injection Methods 0.000 claims abstract description 11
- 239000007924 injection Substances 0.000 claims abstract description 11
- 238000002360 preparation method Methods 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000001412 amines Chemical class 0.000 claims abstract description 5
- 239000003999 initiator Substances 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 5
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000178 monomer Substances 0.000 claims description 20
- MSSNHSVIGIHOJA-UHFFFAOYSA-N pentafluoropropane Chemical compound FC(F)CC(F)(F)F MSSNHSVIGIHOJA-UHFFFAOYSA-N 0.000 claims description 18
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 13
- 229930006000 Sucrose Natural products 0.000 claims description 13
- 239000005720 sucrose Substances 0.000 claims description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- -1 glyceryl alcohol Chemical compound 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 235000011187 glycerol Nutrition 0.000 claims description 7
- 230000003068 static effect Effects 0.000 claims description 7
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 5
- 239000004615 ingredient Substances 0.000 claims description 4
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 4
- MDFFNEOEWAXZRQ-UHFFFAOYSA-N aminyl Chemical compound [NH2] MDFFNEOEWAXZRQ-UHFFFAOYSA-N 0.000 claims description 3
- 238000006116 polymerization reaction Methods 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 150000003918 triazines Chemical class 0.000 claims description 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical class [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 2
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000004088 foaming agent Substances 0.000 abstract 2
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 239000000463 material Substances 0.000 description 6
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 3
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 3
- MEIRRNXMZYDVDW-MQQKCMAXSA-N (2E,4E)-2,4-hexadien-1-ol Chemical compound C\C=C\C=C\CO MEIRRNXMZYDVDW-MQQKCMAXSA-N 0.000 description 2
- 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 description 2
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 2
- 229930195725 Mannitol Natural products 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 239000000594 mannitol Substances 0.000 description 2
- 235000010355 mannitol Nutrition 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- FRCHKSNAZZFGCA-UHFFFAOYSA-N 1,1-dichloro-1-fluoroethane Chemical compound CC(F)(Cl)Cl FRCHKSNAZZFGCA-UHFFFAOYSA-N 0.000 description 1
- 241000197192 Bulla gouldiana Species 0.000 description 1
- XWCDCDSDNJVCLO-UHFFFAOYSA-N Chlorofluoromethane Chemical compound FCCl XWCDCDSDNJVCLO-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 description 1
- 241000009328 Perro Species 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- 229920001247 Reticulated foam Polymers 0.000 description 1
- NSOXQYCFHDMMGV-UHFFFAOYSA-N Tetrakis(2-hydroxypropyl)ethylenediamine Chemical compound CC(O)CN(CC(C)O)CCN(CC(C)O)CC(C)O NSOXQYCFHDMMGV-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- TZMQHOJDDMFGQX-UHFFFAOYSA-N hexane-1,1,1-triol Chemical compound CCCCCC(O)(O)O TZMQHOJDDMFGQX-UHFFFAOYSA-N 0.000 description 1
- 229920005669 high impact polystyrene Polymers 0.000 description 1
- 239000004797 high-impact polystyrene Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000000052 vinegar Substances 0.000 description 1
- 235000021419 vinegar Nutrition 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The present invention discloses polyurethane rigid foam plastics and a preparation method thereof. Polyisocyanate, premixed polyether and a foaming agent are used as raw material; the main component of the premixed polyether is polymonoether with various functionalities of 3 to 8 and the molecular weight under 1300; the polymonoether is generated by polymerizing one kind or many kinds of initiators and propylene oxide. The present invention is characterized in that the premixed polyether has the specific weight portions of components of 100 portions of polymonoether, 2.0 to 2.7 portions of suds stabilizing agents, 1.5 to 2.8 portions of water, 0.8 to 2.0 portions of various amine catalysts and 15 to 25 portions of HFC-245 fa foaming agents. Firstly, the temperature of HFC-245 fa is cooled to 5 to 10 DEG C; then, HFC-245 fa and the premixed polyether composed of many kinds of polymonoether, suds stabilizing agents and catalysts are uniformly mixed and stirred; the polyisocyanate and the mixed premixed polyether are foamed in a high-pressure mixing mode by an injection head through a high-pressure foaming machine; finally, the polyisocyanate and the mixed premixed polyether are poured and foamed under the pressure of 10 to 20Mpa, and the foam plastics with environmental protection and good heat-insulating property is obtained through a maturing and forming process.
Description
Technical field
The present invention relates to the porous plastics technical field, more particularly relate to a kind of polyurethane rigid foam plastic and preparation method thereof.
Background technology
Hard polyurethane foams is a kind of high molecular synthetic material of superior performance, has characteristics such as density is little, intensity is high, thermal conductivity is low, bonding strength is big, is widely used in fields such as refrigerator, refrigerator, thermal container as a kind of heat-insulating material.The preparation method of traditional PU (urethane) porous plastics is to be whipping agent with CFC-11 (3 chloro-fluoromethane), whipping agent and combined polyether are mixed, by injection head and MDI (diphenylmethane diisocyanate vinegar) high pressure mixing, high-pressure injection is to specific regions such as refrigerator body intermediate courses then.After the material feeding, whipping agent is converted into gas by liquid under the high temperature that generates PU reaction generation, produce a large amount of bubbles, makes polyether polyols with reduced unsaturation generate the reticulated foams structure, forms porous plastics.But CFC-11 in use has part and is discharged in the atmosphere as whipping agent, and the ozonosphere in the atmosphere is destroyed, and for preserving our planet, international environmental protection organization proposes the forbidding requirement to materials such as CFC-11.China is the contracting states of Montreal Agreement and CFC, HCFC, CCl
4Deng the production of ozone layer depletion thing with consume big country, the research of CFC surrogate have been carried out for many years, and along with new efficiency standard forces to carry out, the applied research of carrying out the surrogate of a kind of not only energy-conservation but also environmental protection seems urgent more.In the refrigerator industry, surrogate as CFC-11 mainly contains HCFC141b and pentamethylene, the ODP ODP=0.11 of HCFC141b, still atmospheric ozone layer there is certain destructiveness, pentamethylene does not have influence to ozonosphere, be present main surrogate, but shortcomings such as that pentamethylene exists is inflammable and explosive, poor insulation property.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of polyurethane rigid foam plastic and preparation method thereof, it adopts the monomer polyethers is main raw material, add non-combustible whipping agent, foaming and use do not have destruction to atmospheric ozone layer and guarantee the quality and the heat-insulating property of foam article.
Above-mentioned technical problem solves like this, construct a kind of polyurethane rigid foam plastic, raw materials used is polyisocyanates, combined polyether and whipping agent, the combined polyether major ingredient is that multiple functionality is 3～8, the monomer polyethers of molecular weight below 1300, the monomer polyethers is to be generated by one or more initiators and propylene oxide polymerization, the concrete parts by weight of each component are in the aforesaid combination polyethers, monomer polyethers: 100 parts, suds-stabilizing agent: 2.0～2.7 parts, water: 1.5～2.8 parts, all kinds of amines catalysts: 0.8～2.0 part, HFC-245fa whipping agent: 15～25 parts.
The preparation method of above-mentioned porous plastics comprises following operation:
(1) HFC-245fa is cooled to 5-15 ℃;
(2) combined polyether that HFC-245fa and multiple monomer polyethers, suds-stabilizing agent, catalyzer are formed mixes and stirs;
(3) polyisocyanates foams with the injection head high pressure mixing by high pressure foaming machine with the combined polyether that mixes;
(4) high pressure bubble injecting, pressure are 10-20Mpa.
(5) maturing process, moulding, the demoulding.
The preparation method of above-mentioned porous plastics also can comprise following operation:
(1) becomes combined polyether by multiple monomer polyethers, suds-stabilizing agent, catalyst mix;
(2) combined polyether and the temperature range HFC-245fa at 15～22 ℃ is mixed by static mixer;
(3) in high pressure foaming machine with the polyisocyanates high pressure mixing;
(4) with the foaming of injection head high pressure mixing;
(5) high pressure bubble injecting, pressure are 10-20Mpa;
(6) slaking, moulding, the demoulding.
The present invention compared with prior art has the following advantages and beneficial effect:
1.HFC-245fa belong to non-VOC class material, harmless to ozonosphere, ODP=0 is a kind of ideal surrogate.
2. the porous plastics thermal conductivity with the HFC-245fa foaming is low, and refrigerator energy-saving is effective, and especially at low temperatures, energy consumption of refrigerator has more superiority.
3.HFC-245fa not flammable, compare with other present alternative whipping agent, be the whipping agent of heat-insulating property the best.
4.HFC-245fa common plastics (ABS, HIPS) is not had erosion, can not damage inner bag, be one of optimum substituent of HCFC-141b.
Embodiment
Polyurethane rigid foam plastic of the present invention, raw materials used is polyisocyanates, combined polyether and whipping agent, the combined polyether major ingredient is that multiple functionality is 3～8, the monomer polyethers of molecular weight below 1300, the monomer polyethers is to be generated by one or more initiators and propylene oxide polymerization, and used initiator is chosen from following material: glycerine, propylene glycol, hexanetriol, TriMethylolPropane(TMP), quadrol, sorbyl alcohol, sucrose, xylidene(s), N.F,USP MANNITOL etc.Monomer polyethers commonly used contains several following monomer polyethers: amidogen ether, glyceryl alcohol polyethers, sucrose polyethers, N.F,USP MANNITOL polyethers, sorbyl alcohol polyethers, glycerine sucrose polyethers, xylidene(s) polyethers, polyester polyethers etc.The concrete parts by weight of each component are in combined polyether, the monomer polyethers: 100 parts, and suds-stabilizing agent: 2.0～2.7 parts, water: 1.5～2.8 parts, all kinds of amines catalysts: 0.8～2.0 part, HFC-245fa whipping agent: 15～25 parts.Three cluster catalyzer can be from sylvite class catalyzer (as the ethylene glycol solution of sad first, Potassium ethanoate), triazines catalyzer (as C-41) or quaternary ammonium salts catalyzer (as the TMR series of airproducts company).
Embodiment 1
The mixture that mixed preparing is made up of multiple monomer polyethers in 1000 liters of combined polyether storage tanks is cooled to 5～10 ℃ with 20 parts of HFC-245fa, puts into the interior premix of the combined polyether storage tank for preparing combined polyether to be housed 30 minutes.The composition of mixture in jar that multiple monomer polyethers is formed is: 10 parts of amidogen ethers (hydroxyl value 700～770), 9 parts of glyceryl alcohol polyethers (hydroxyl value 330～350), 21 parts of sucrose polyethers (hydroxyl value 420～450), 38 parts of glycerine sucrose polyethers (hydroxyl value 400～450), other adds suds-stabilizing agent, water, catalyzer is an amount of, concrete weight deal is: suds-stabilizing agent: 2.3～2.5 parts, water: 1.5～2.6 parts, various amines catalysts add up to 0.8～2.0 part, usually select 3～4 kinds for use, can be: 0.05～0.13 part of dimethylin sulfuric ether (or pentamethyl-diethylenetriamine), N, N-dimethylcyclohexylamine: 0.3～0.6 part, contain the diethylene glycol solution of triethylene diamine 33%: 0.7～1.0 part, triazines catalyzer: 0.4～0.6 part.The material temperature of foaming process is controlled at 15～22 ℃, 110 parts of polyisocyanates (deal of polyisocyanates is controlled in 1～1.3 times the scope of above-mentioned each component total amount) in foaming process, injection head by high pressure foaming machine is under 11～16Mpa pressure, with the mixture high pressure mixing foaming of above-mentioned HFC-245fa that has been mixed and combined polyether, wherein freely steep density: 23～26kg/m
3, core density: 29～35kg/m
3, expansion rate is controlled at: cream time 0～5s, and gel time 60 ± 10s, the foaming mould temperature is controlled at 30～50 ℃, workpiece surface temperature 〉=30 ℃.Bubble material by high-pressure injection to the refrigerator body intermediate course, after overcuring drying tunnel operation, moulding, the demoulding, the product after obtaining foaming.
Embodiment 2
Earlier prepare combined polyether in in-tank mixing, deal is: 11 parts of amidogen ethers (hydroxyl value 700～770), 10 parts of glyceryl alcohol polyethers (hydroxyl value 330～350), 22 parts of sucrose polyethers (hydroxyl value 420～450), 40 parts of glycerine sucrose polyethers (hydroxyl value 400～450), the deal of suds-stabilizing agent, catalyzer, water is identical with embodiment 1.With temperature is 15～22 ℃ 24 parts of the HFC-245fa whipping agents and the MEF static mixer (pressure≤1.5Mpa of the above-mentioned combined polyether injection Cannon company for preparing, flow 30～45L/min), static mixer also can adopt the static mixer product of companies such as Hennecke, OMS or Perros, foam by high pressure foaming machine injection head high pressure mixing with polyisocyanates (deal is identical with embodiment 1) then, remaining operation is identical with embodiment 1.
Claims (8)
1. polyurethane rigid foam plastic, raw materials used is polyisocyanates, combined polyether and whipping agent, the combined polyether major ingredient is that multiple functionality is 3～8, the monomer polyethers of molecular weight below 1300, the monomer polyethers is to be generated by one or more initiators and propylene oxide polymerization, it is characterized in that: the concrete parts by weight of each component are in the described combined polyether, monomer polyethers: 100 parts, suds-stabilizing agent: 2.0～2.7 parts, water: 1.5～2.8 parts, all kinds of amines catalysts: 0.8～2.0 part, HFC-245fa whipping agent: 15～28 parts; Wherein the concrete composition of monomer polyethers and parts by weight are amidogen ether: 6～16 parts, and the glyceryl alcohol polyethers: 6～13 parts, the sucrose polyethers: 16～25 parts, glycerine sucrose polyethers: 35～46 parts.
2. porous plastics according to claim 1, it is characterized in that: the parts by weight as the monomer polyethers of combined polyether major ingredient are: amidogen ether: 9～13 parts, glyceryl alcohol polyethers: 8～10 parts, sucrose polyethers: 20～23 parts, glycerine sucrose polyethers: 37～43 parts, suds-stabilizing agent: 2.3～2.5 parts, water: 1.8～2.6 parts, dimethylin sulfuric ether: 0.05～0.13 part, N, the N-dimethylcyclohexylamine: 0.3～0.6 part, the diethylene glycol solution of 33% triethylene diamine: 0.5～1.0 part, three cluster catalyzer: 0.4～0.6 part, HFC-245fa:16～22 part.
3. porous plastics according to claim 2 is characterized in that: amidogen ether hydroxyl value scope is 700～770, glyceryl alcohol polyethers hydroxyl value scope 330～350, sucrose polyethers hydroxyl value scope 420～450, glycerine sucrose polyethers hydroxyl value scope 400～450.
4. porous plastics according to claim 2 is characterized in that: described three cluster catalyzer are sylvite class catalyzer or triazines catalyzer or quaternary ammonium salts catalyzer.
5. the preparation method of the polyurethane rigid foam plastic of claim 1 is characterized in that comprising following operation:
(1) HFC-245fa is cooled to 5-15 ℃;
(2) combined polyether that HFC-245fa and multiple monomer polyethers, suds-stabilizing agent, catalyzer are formed mixes and stirs;
(3) polyisocyanates foams with the injection head high pressure mixing by high pressure foaming machine with the combined polyether that mixes;
(4) high pressure bubble injecting, pressure are 10-20Mpa.
(5) maturing process, moulding, the demoulding.
6. the preparation method of porous plastics according to claim 5 is characterized in that it is 30 minutes that HFC-245fa and combined polyether mix the time of stirring, and mixing temperature is 15-22 ℃.
7. the preparation method of the polyurethane rigid foam plastic of claim 1 is characterized in that comprising following operation:
(1) becomes combined polyether by multiple monomer polyethers, suds-stabilizing agent, catalyst mix;
(2) combined polyether and the temperature range HFC-245fa at 15～22 ℃ is mixed by static mixer;
(3) in high pressure foaming machine with the polyisocyanates high pressure mixing;
(4) with the foaming of injection head high pressure mixing;
(5) high pressure bubble injecting, pressure are 10-20Mpa;
(6) slaking, moulding, the demoulding.
8. the preparation method of porous plastics according to claim 7 is characterized in that described static mixer is the MEF static mixer of Cannon.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2003101121772A CN1301279C (en) | 2003-11-14 | 2003-11-14 | Polyurethane hard foamed plastics and its preparing method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2003101121772A CN1301279C (en) | 2003-11-14 | 2003-11-14 | Polyurethane hard foamed plastics and its preparing method |
Publications (2)
| Publication Number | Publication Date |
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| CN1616512A CN1616512A (en) | 2005-05-18 |
| CN1301279C true CN1301279C (en) | 2007-02-21 |
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| CNB2003101121772A Expired - Lifetime CN1301279C (en) | 2003-11-14 | 2003-11-14 | Polyurethane hard foamed plastics and its preparing method |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1995109B (en) * | 2006-01-06 | 2011-04-27 | 广东科龙电器股份有限公司 | Process for preparing rigid polyurethane foams |
| CN101838459A (en) * | 2010-05-24 | 2010-09-22 | 安徽省思维新型建材有限公司 | Rigid polyurethane foam plastic and preparation method thereof |
| CN102443134B (en) * | 2011-09-16 | 2013-08-07 | 广东万华容威聚氨酯有限公司 | Polyurethane rigid foam and preparation method thereof |
| CN105542427A (en) * | 2015-12-24 | 2016-05-04 | 青岛海尔股份有限公司 | Refrigerator sealing part, refrigerator backplate component and molding method and refrigerator |
| JP6926660B2 (en) * | 2016-05-17 | 2021-08-25 | 東ソー株式会社 | Amine catalyst composition for the production of haloalkene foamed polyurethane |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1199058A (en) * | 1997-05-08 | 1998-11-18 | 气体产品与化学公司 | Silicone surfactants for rigid polyurethane foam made with third generation blowing agents |
-
2003
- 2003-11-14 CN CNB2003101121772A patent/CN1301279C/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1199058A (en) * | 1997-05-08 | 1998-11-18 | 气体产品与化学公司 | Silicone surfactants for rigid polyurethane foam made with third generation blowing agents |
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| CN1616512A (en) | 2005-05-18 |
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