CN101531753B - MDI-group isocyanate composition and soft mould foamed plastic - Google Patents
MDI-group isocyanate composition and soft mould foamed plastic Download PDFInfo
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- CN101531753B CN101531753B CN 200910081573 CN200910081573A CN101531753B CN 101531753 B CN101531753 B CN 101531753B CN 200910081573 CN200910081573 CN 200910081573 CN 200910081573 A CN200910081573 A CN 200910081573A CN 101531753 B CN101531753 B CN 101531753B
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Abstract
The invention discloses an MDI-group isocyanate composition and a cold set type soft mould foamed plastic. The composition is generated by the reaction of the following components according to 100wt%: (1) polymethylene polyphenyl polyisocyanate of 70-97wt%; (2) carbodiimide and/or uretonimine modified diphenylmethane diisocyanates; and (3) polyether glycol with the content of oxide ethylidene group of 7-76wt% or a mixture composed of a) polyether glycol with the content of oxide ethylidene group over 50wt% and b) polyether glycol with the content of oxide ethylidene group of 10-20wt%. The invention has excellent technique processing characteristic, avoids the cracking and collapsing during shrinking and rolling, in particular the soft mould foamed plastic has excellent compression deformation performance and the MDI-group isocyanate composition is unlikely to crystallize in low temperature storage.
Description
Technical field
The present invention relates to a kind of new MDI group isocyanate composition, reach the cold curing soft mould foamed plastic of making by the MDI group isocyanate composition.
Background technology
Based on the vulcabond of '-diphenylmethane diisocyanate MDI and the mixture of polymethylene many (phenyl isocyanate) (being polymeric MDI or PMD1), and be known based on the prepolymer of this mixture, and describe in the prior art.Use these based on the vulcabond of MDI and the mixture of polymeric MDI or PMDI, and also be known based on the method that the prepolymer of this mixture is made flexible polyurethane foam.
U.S. Pat 5877227 disclosed polyisocyantates compositions contain a kind of semi prepolymer, and it is fill a prescription substantially a reaction product with 5-50% (weight) the first polyoxyethylene polyoxypropylene polyvalent alcohol (nominal functionality is that 2-4, molecular weight are that 1000-8000, EO content are about 0-30% (weight)) of excessive isocyanic ester.The mixture that comprises MDI and PMDI during this isocyanic ester is filled a prescription substantially; Disclosing this polyisocyantates composition is adapted to pass through with reacting with the composition of isocyanate reaction with as the water of unique whipping agent and prepares the open cell type flexible polyurethane foam.This prepolymer has only used the polyvalent alcohol of oxyethane (EO) content 0-30% (weight).
U.S. Pat 6077456 also discloses the liquid polyisocyanate prepolymer composite.The NCO group content of these prepolymers is 10-31%, and contains the reaction product of organic multiple isocyanate mixture and polyoxy sub alkyl polylol.This polyisocyanate mixtures comprises: A) contain 4 of 50-95% (weight), 4 '-isomer, 5-50% (weight) 2,4 '-isomer and be less than 10% (weight) 2, the '-diphenylmethane diisocyanate of 2 '-isomer; B) contain the poly methylene poly phenyl poly isocyanate of 30-70% (weight) MDI, all the other are PMDI, functionality is greater than 2, and C) randomly, the vulcabond that contains 10-35% (weight) uretonimine (uretonimine) carbodiimide modification, remaining is mainly by pure 4, and 4 '-MDI constitutes.The polyoxy sub alkyl polylol that is applicable to this method comprises that molecular weight is that 700-10000 and average functionality are the polyvalent alcohol of 1.6-3.
United States Patent (USP) 6090864 discloses polymeric MDI prepolymer composite and the application in the preparation flexible foam plastic thereof.These prepolymers comprise the reaction product that poly methylene poly phenyl poly isocyanate and average light basic equivalent are at least about 700 polyether glycol, and the average viscosity under its 25 ℃ is 400-7000CPs.
Chinese patent CN02805527.6 discloses a kind of method of making flexible polyurethane foam, this method makes prepolymer and flexible PU foam has following technological deficiency: the functionality that does not have clear and definite prepolymer, the content that does not also have clear and definite polymkeric substance methylene diphenyl isocyanate, especially the content of dimethylene triphenyl triisocyanate and the above poly methylene poly phenyl poly isocyanate of three phenyl ring, the prepolymer that this method makes causes foam collapse easily in the soft bubble of the high resilience molding of preparation, and this defective is at automobile, furniture is with being flagrant in the soft bubble.
Summary of the invention
At above technological deficiency, the invention provides a kind of new MDI group isocyanate composition, and cold curing soft mould foamed plastic that makes by described MDI group isocyanate composition and their preparation method.
The nco value of MDI group isocyanate composition provided by the present invention is that 25-32%, functionality are 2.05-2.3, and described composition is mainly generated by following component reaction:
(1) in (1) and (2) of 100 weight %, the poly methylene poly phenyl poly isocyanate of 70-97wt%, wherein, monomer kind isocyanate content in the described poly methylene poly phenyl poly isocyanate is 10-88 weight %, the tricyclic antidepressants isocyanate content is 4-20 weight %, and the above kind isocyanate content of three rings is 3-15 weight %; Wherein, described monomer kind isocyanate is meant '-diphenylmethane diisocyanate; Described tricyclic antidepressants isocyanic ester is meant dimethylene triphenyl triisocyanate; The above kind isocyanate of described three rings is meant N methylene radical N phenyl N isocyanic ester (N is greater than 3).The preferred described '-diphenylmethane diisocyanate of the present invention is by the composition of 4,4 of 2,4 of 2,2 of 0-5 weight % '-'-diphenylmethane diisocyanate, 4-48 weight % '-'-diphenylmethane diisocyanate and 52-95 weight % '-'-diphenylmethane diisocyanate;
(2) in (1) and (2) of 100 weight %, the carbodiimide of 3-30 weight % and/or uretonimine-modified '-diphenylmethane diisocyanate; With
(3) oxygen ethylidene content is the polyether glycol of 7-76 weight %; Or by a) oxygen ethylidene content greater than polyether glycol and the b of 50 weight %) oxygen ethylidene content is the mixture of the polyether glycol formed of the polyether glycol of 10-20 weight %, wherein a) polyether glycol and b) weight ratio of polyether glycol is 10: 60-60: 10; Be preferably 15: 70-85: 30.
In the MDI group isocyanate composition of the present invention, in the described component (3), oxygen ethylidene content is that the polyether glycol of 7-76 weight % is: average nominal hydroxy functionality is that 2-8, average equivalent are that 800-3000, molecular-weight average are that the oxygen ethylidene content of 2400-10000 is the polyether glycol of 7-76 weight %;
In the MDI group isocyanate composition of the present invention, described a) the oxygen ethylidene content in the component (3) greater than the polyether glycol of 50 weight % is: average nominal hydroxy functionality is that 2-8, average equivalent are that 800-3000, molecular-weight average are the polyether glycol of the oxygen ethylidene content of 2400-10000 greater than 50 weight %;
In the MDI group isocyanate composition of the present invention, the described b in the component (3)) oxygen ethylidene content is that the polyether glycol of 10-20 weight % is: average nominal hydroxy functionality is that 2-8, average equivalent are that 800-3000, molecular-weight average are that the oxygen ethylidene content of 2400-10000 is the polyether glycol of 10-20 weight %.
The prepared MDI isocyanate composition of the present invention is isocyanate-terminated prepolymer.
The present invention also provides a kind of soft mould foamed plastic, described plastics by the MDI isocyanate composition among the present invention and isocyanate-reactive composition in the presence of the water, isocyanate index is to react under the 60-120 condition to make.Described isocyanate-reactive composition is made of following component: by weight percentage, c) polyether glycol of 80-100 weight %, its average nominal functionality is 2-8, and average equivalent is 750-5000, and molecular-weight average is that 2000-12000 and oxygen ethylidene content are 10-30wt%; And d) water, additive and the auxiliary agent of 0-20 weight %.
The soft mould foamed plastic that the present invention produces can adopt the method for this area routine to be prepared, as nonrestrictive use moulding technology, promptly allowing foams rise in airtight mould sends out, the example of this mould is industrial be used to make polyurethane furniture parts, automobile cushion and other auto parts, as headrest, sound insulating pad etc.Example of moulding technology is a kind of moulding technology that is called cold-curing, and wherein die temperature is at 40-80 ℃, preferred 50-60 ℃ temperature, and foam solidified 2-10 minute therein, foams slaking at normal temperatures 1 hour to 2 days usually after the demoulding.
Amount of component b in the isocyanate-reactive composition of the present invention) polyether glycol can be polyether glycol that comprises ester group or the polyether glycol that comprises amine groups.Preferred polyether glycol comprises the polyether glycol that obtains in the condensation that contains on (beginning thing) compound of at least two active hydrogen atoms by the alkene oxide that contains 2-6 carbon atom, wherein, alkene oxide is oxyethane, propylene oxide, or the compound of oxyethane or propylene oxide units can be provided in polyether glycol.
The suitable beginning thing polyvalent alcohol of isocyanate-reactive composition of the present invention can for glycol, triol, tetrol, amine, alkanolamine or polyamine etc., and composition thereof.The polyether glycol of isocyanate-reactive composition of the present invention comprises oxyethane and/or propylene oxide suitably, beginning thing polyvalent alcohol is selected from glycol, for example dipropylene glycol, triol glycerine and TriMethylolPropane(TMP), tetrol tetramethylolmethane, diamines quadrol, aromatic amine ortho-toluene diamine, alkanolamine for example Xylitol, arabitol, Sorbitol Powder and mannitol of trolamine and multifunctional hydroxyl alkane for example for example for example for example for example.The polyether glycol of isocyanate-reactive composition of the present invention can use with pure product, maybe can comprise solids, and the preferred polymers particle uses.Particle is in the dispersion suitably or part is connected on the polyvalent alcohol chain, and size is less than 20 microns.The polymkeric substance that is particularly suitable for this purpose comprises polyacrylonitrile, polystyrene, polyvinyl chloride, comprises the multipolymer and the urea groups polymkeric substance of any of these polymkeric substance.These solids can be in polyvalent alcohol in-situ polymerization and preparing, or preparation and joining in the polyvalent alcohol then separately.
The present invention prepares in the soft mould foamed plastic of the present invention, and whipping agent can only make water, also the inferior whipping agent of water and non-chlorofluoro-alkane can be united use, and preferably the usage quantity of water is greater than the usage quantity of any other whipping agent.Because the formation by its urea key is relevant with carbon dioxide generating, carbonic acid gas can excite the foaming/swell process of urethane resin, therefore obtains flexible foamed urethane, and water has key function in the preparation of polyurathamc.With respect to 100 parts by weight of component c) polyether polyols, the usage quantity of preferably water is the 3-6 weight part, the present invention can use the blown with carbon dioxide urethane resin, preferably as by reaction water and polyisocyanates NCO group and the main foaming agent that original position produces.
Isocyanate-reactive composition of the present invention can comprise that one or more are generally used for the additive or the auxiliary agent of polyurathamc preparation, operable additive or auxiliary agent include but not limited to tensio-active agent, amine catalyst and alcamines linking agent, wherein, for example diethanolamine, trolamine etc. of alcamines linking agent; Amine catalyst, as triethylenediamine, metallic material such as stannous octoate, abscess conditioning agent, thermal oxidation stabilizer, pigment etc.
Compared with prior art, have better suitable perforate, avoided the cracking in contraction and the roll extrusion process, certain stability is arranged again, avoided collapsing bubble and unnecessary defective by MDI group isocyanate composition soft mould foamed plastic of the present invention.
The high-elastic foam plastic that certain supporting capacity is arranged that MDI group isocyanate composition of the present invention and soft mould foamed plastic can be used for using in automobile, the furniture.Be characterized in having good processes characteristic, avoided the cracking in contraction and the roll extrusion process, certain stability has been arranged again, avoided collapsing bubble and unnecessary defective, and good especially compression set performance of physicals is arranged, and in low-temperature storage, be difficult for crystallization.
Embodiment
The present invention is further illustrated by following examples in the present invention, but the present invention is not limited to this.
Embodiment 1-8 is the preparation of MDI group isocyanate composition
In following examples,
Polyethers A: molecular-weight average is 6000, and functionality is 3 oxyethane propylene oxide based polyether polyol, and wherein the EO/P0 ratio is 15/85;
Polyethers B: molecular-weight average is 5000, and functionality is 3 oxyethane propylene oxide based polyether polyol, and wherein the EO/P0 ratio is 75/25.
Embodiment 1
Prepare isocyanate composition by reacting following material: the poly methylene poly phenyl poly isocyanate of 85 weight parts, numbering PM-1, with the polyethers A of 8.0 weight parts, the polyethers B of 7.0 weight parts, under 70-80 ℃, carry out about 2 hours reaction, obtain 27.76% free NCO content.Poly methylene poly phenyl poly isocyanate wherein, the composition of numbering PM-1 sees Table 1.
Embodiment 2
Prepare isocyanate composition by reacting following material: the poly methylene poly phenyl poly isocyanate of 85 weight parts, numbering PM-2, with the polyethers A of 8.0 weight parts, the polyethers B of 7.0 weight parts, under 70-85 ℃, carry out about 2 hours reaction, carbodiimide modification MDI with 8 weight parts joins in the prepolymer then, obtains 27.39% free NCO content.Poly methylene poly phenyl poly isocyanate wherein, the composition of numbering PM-2 sees Table 1.
Embodiment 3-8 is by preparing isocyanate composition by the material in the table 2: the weight represented according to table 2 adds poly methylene poly phenyl poly isocyanate, carbodiimide modification MDI, carry out about 2 hours reaction with polyethers A, the polyethers B of the represented weight part of table 2 under 70-85 ℃, the NCO% of gained MDI group isocyanate composition sees Table 2.
The composition of table 1 poly methylene poly phenyl poly isocyanate
| The numbering of poly methylene poly phenyl poly isocyanate | PM-1 | PM-2 | PM-3 | PM-4 | PM-5 | PM-6 | PM-7 | PM-8 |
| 4，4-MDI | 55.55 | 47.55 | 40.55 | 30.55 | 61.1 | 56.1 | 51.1 | 41.1 |
| 2，4-MDI | 20.60 | 20.60 | 20.60 | 20.60 | 6.20 | 6.20 | 6.20 | 6.20 |
| Dimethylene trimethylphenyl triisocyanate | 5.07 | 5.07 | 5.07 | 5.07 | 10.14 | 10.14 | 10.14 | 10.14 |
| Four phenyl ring and above isocyanic ester | 3.78 | 3.78 | 3.78 | 3.78 | 7.56 | 7.56 | 7.56 | 7.56 |
Table 2MDI group isocyanate composition
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | |
| Prepolymer-1 | Prepolymer-2 | Prepolymer-3 | Prepolymer-4 | Prepolymer-5 | Prepolymer-6 | Prepolymer-7 | Prepolymer-8 | |
| PM-1 | 85 | |||||||
| ?PM-2 | 77 | |||||||
| ?PM-3 | 70 |
| ?PM-4 | 60 | |||||||
| ?PM-5 | 85 | |||||||
| ?PM-6 | 80 | |||||||
| ?PM-7 | 75 | |||||||
| ?PM-8 | 65 | |||||||
| Carbodiimide modification MDI | 0.0 | 8.0 | 15.0 | 25.0 | 0.0 | 5 | 10 | 20 |
| Polyethers A | 8.0 | 8.0 | 8.0 | 8.0 | 8.0 | 8 | 8 | 8 |
| Polyethers B | 7 | 7 | 7 | 7 | 7 | 7 | 7 | 7 |
| ?NCO％ | 27.76 | 27.39 | 27.07 | 26.61 | 27.29 | 27.06 | 26.83 | 26.37 |
Embodiment 9-16 is the preparation of soft mould foamed plastic
In following examples,
Polyethers C: the initial poly(propylene oxide) oxyethane of glycerine ether, average functionality 3, hydroxyl value 35.Plant of Tianjin Petrochemical Company three factories, trade mark TEP330N.
B8715: the high resilient surface promoting agent of Gao Shi Mitt USA Corporation.
DEOA: the pure diethanolamine in commercial reagent.
Varies catalyzer: A-1: Mai Tu company amine catalyst; A-33: Mai Tu company amine catalyst; D8154: gas companies amine catalyst.
Embodiment of the invention 9-16 preparation is adopted as the material in the table 3 and is adopted following method preparation: the cold-curing moulding technology, die temperature is 55 ℃ temperature, foam solidified 4 minutes therein, foams slaking at normal temperatures 1 day usually after the demoulding, and the performance of gained soft mould foamed plastic sees Table 3.
The soft mould foamed plastic that table 3 isocyanate prepolymer makes
| Embodiment-9 | Embodiment-10 | Embodiment-11 | Embodiment-12 | Embodiment-13 | Embodiment-14 | Embodiment-15 | Embodiment-16 | |
| Polyethers C | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 |
| Water | 3.5 | 3.5 | 3.5 | 3.5 | 3.5 | 3.5 | 3.5 | 3.5 |
| DEOA | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| B8715 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| A-1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 |
| A33 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
| D8154 | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 |
| Isocyanic ester | Prepolymer-1 | Prepolymer-2 | Prepolymer-3 | Prepolymer-4 | Prepolymer-5 | Prepolymer-6 | Prepolymer-7 | Prepolymer-8 |
| Index | 95 | 95 | 95 | 95 | 95 | 95 | 95 | 95 |
| Density kg/m 3 | 50.1 | 51.9 | 52.4 | 50.7 | 51.8 | 50.0 | 49.2 | 50.4 |
| Tensile strength/KPa | 101 | 129 | 143 | 141 | 112 | 121 | 122 | 118 |
| Elongation | 104.2 | 108.5 | 118 | 120 | 95.8 | 97.2 | 95.5 | 92.9 |
| Tear strength N/cm | 2.56 | 2.97 | 2.88 | 2.50 | 2.24 | 2.29 | 2.35 | 1.99 |
| CLD40％KPa | 4.3 | 5.0 | 4.5 | 3.7 | 5.9 | 5.5 | 5.6 | 5.1 |
| Dry compression distortion 50% | 2.6 | 2.7 | 2.6 | 3.1 | 3.0 | 5.2 | 6.5 | 7.5 |
As can be seen from Table 3, soft mould foamed plastic of the present invention has better suitable perforate, has avoided the cracking in contraction and the roll extrusion process, certain stability is arranged again, avoided collapsing and steeped and unnecessary defective, and physicals aspect comparison balance, every index is all better.
Claims (9)
1. MDI group isocyanate composition, the nco value of described composition is that 25-32%, functionality are 2.05-2.3, described composition is mainly generated by following component reaction:
(1) in (1) and (2) of 100 weight %, the poly methylene poly phenyl poly isocyanate of 70-97%, wherein, monomer kind isocyanate content in the poly methylene poly phenyl poly isocyanate of described 70-97% is 10-88 weight %, the tricyclic antidepressants isocyanate content is 4-20 weight %, the above kind isocyanate content of three rings is 3-15 weight %, wherein, described monomer kind isocyanate is meant '-diphenylmethane diisocyanate, described tricyclic antidepressants isocyanic ester is meant dimethylene triphenyl triisocyanate, the above kind isocyanate of described three rings is meant N methylene radical N isocyanic ester, and wherein N is greater than 3;
(2) in (1) and (2) of 100 weight %, the carbodiimide modified diphenylmethane vulcabond of 3-30wt% and/or uretonimine-modified '-diphenylmethane diisocyanate; With
(3) oxygen ethylidene content is the polyether glycol of 7-76 weight %; Or by a) oxygen ethylidene content greater than polyether glycol and the b of 50 weight %) oxygen ethylidene content is the mixture of the polyether glycol formed of the polyether glycol of 10-20 weight %, and a) polyether glycol and b) weight ratio of polyether glycol is 10: 60-60: 10.
2. MDI group isocyanate composition according to claim 1, it is characterized in that, in the component (1), described monomer kind isocyanate is by 2 of 0-5 weight %, 2 '-'-diphenylmethane diisocyanate, 4-48 weight % 2,4 '-'-diphenylmethane diisocyanate and 52-95 weight % 4,4 '-composition of '-diphenylmethane diisocyanate.
3. MDI group isocyanate composition according to claim 2, it is characterized in that, in the component (3), the polyether glycol that described oxygen ethylidene content is 7-76% is: average nominal hydroxy functionality is that 2-8, average equivalent are that 800-3000, molecular-weight average are that the oxygen ethylidene content of 2400-10000 is the polyether glycol of 7-76%.
4. MDI group isocyanate composition according to claim 3, it is characterized in that, in the component (3), described component a) oxygen ethylidene content greater than the polyether glycol of 50 weight % is: average nominal hydroxy functionality is that 2-8, average equivalent are that 800-3000, molecular-weight average are the polyether glycol of the oxygen ethylidene content of 2400-10000 greater than 50 weight %.
5. MDI group isocyanate composition according to claim 4, it is characterized in that, in the component (3), described b) oxygen ethylidene content is that the polyether glycol of 10-20 weight % is: average nominal hydroxy functionality is that 2-8, average equivalent are that 800-3000, molecular-weight average are that the oxygen ethylidene content of 2400-10000 is the polyether glycol of 10-20 weight %.
6. MDI group isocyanate composition according to claim 1 is characterized in that, described a) polyether glycol and b) weight ratio of polyether glycol is 15: 70-85: 30.
7. soft mould foamed plastic, it is characterized in that, described porous plastics by the arbitrary described MDI isocyanate composition of claim 1-6 and isocyanate-reactive composition in the presence of the water, isocyanate index is to react under the 60-120 condition to make, described isocyanate-reactive composition is made of following component: by weight percentage
C) polyether glycol of 80-100 weight %, its average nominal hydroxy functionality is 2-8, and average equivalent is 750-5000, and molecular-weight average is that 2000-12000 and oxygen ethylidene content are 10-30 weight %; With
D) water of 0-20 weight %, additive and auxiliary agent.
8. soft mould foamed plastic according to claim 7 is characterized in that, described additive or auxiliary agent are one or more in tensio-active agent, amine catalyst and the alcamines linking agent.
9. soft mould foamed plastic according to claim 8 is characterized in that, described alcamines linking agent is diethanolamine or trolamine; Described amine catalyst is a triethylenediamine.
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| CN106414533B (en) * | 2014-05-29 | 2020-03-13 | 陶氏化学墨西哥股份公司 | Formulation for producing polyurethane foam |
| EP3819323A1 (en) * | 2019-11-07 | 2021-05-12 | Evonik Operations GmbH | Compression set |
| CN116265504A (en) * | 2021-12-16 | 2023-06-20 | 长华化学科技股份有限公司 | Modified isocyanate and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1100030A (en) * | 1993-09-10 | 1995-03-15 | 唐化学原料公司 | Polyurethane foam moldings |
| US6077456A (en) * | 1992-05-12 | 2000-06-20 | Basf Corporation | Polymethylene polyphenyl polyisocyanate based prepolymers |
| US6090864A (en) * | 1997-04-25 | 2000-07-18 | Basf Corporation | Polymeric MDI prepolymer composition and flexible foams prepared therefrom |
| US20060025488A1 (en) * | 2004-07-29 | 2006-02-02 | Stearns Robert B | Composition and process for forming a flexible polyurethane foam sealing device |
| CN1821221A (en) * | 2006-03-08 | 2006-08-23 | 北京科聚化工新材料有限公司 | Poly methylene poly phenyl poly isocyanate with anti-scaling property and preparing method |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6077456A (en) * | 1992-05-12 | 2000-06-20 | Basf Corporation | Polymethylene polyphenyl polyisocyanate based prepolymers |
| CN1100030A (en) * | 1993-09-10 | 1995-03-15 | 唐化学原料公司 | Polyurethane foam moldings |
| US6090864A (en) * | 1997-04-25 | 2000-07-18 | Basf Corporation | Polymeric MDI prepolymer composition and flexible foams prepared therefrom |
| US20060025488A1 (en) * | 2004-07-29 | 2006-02-02 | Stearns Robert B | Composition and process for forming a flexible polyurethane foam sealing device |
| CN1821221A (en) * | 2006-03-08 | 2006-08-23 | 北京科聚化工新材料有限公司 | Poly methylene poly phenyl poly isocyanate with anti-scaling property and preparing method |
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Address after: 102200, Beijing, Changping science and Technology Park Spark Street, No. 5, Beijing poly chemical new material Co., Ltd. Patentee after: Keju Chemical New Material Co., Ltd., Beijing Patentee after: Wanhua Chemical Group Co., Ltd. Address before: 102200, Beijing, Changping science and Technology Park Spark Street, No. 5, Beijing poly chemical new material Co., Ltd. Patentee before: Keju Chemical New Material Co., Ltd., Beijing Patentee before: Yantai Wanhua Polyurethane Co., Ltd. |
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| C56 | Change in the name or address of the patentee |
Owner name: WANHUA CHEMICAL (BEIJING) CO., LTD. Free format text: FORMER NAME: KEJU CHEMICAL NEW MATERIAL CO., LTD., BEIJING |
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| CP03 | Change of name, title or address |
Address after: 102200 No. 5 Spark Street, Changping science and Technology Park, Beijing Patentee after: Wanhua chemical (Beijing) Co., Ltd. Patentee after: Wanhua Chemical Group Co., Ltd. Address before: 102200, Beijing, Changping science and Technology Park Spark Street, No. 5, Beijing poly chemical new material Co., Ltd. Patentee before: Keju Chemical New Material Co., Ltd., Beijing Patentee before: Wanhua Chemical Group Co., Ltd. |