AU605240B2 - Neutralization of polyalkalene carbonate polyols for polyurethane prepolymer synthesis - Google Patents
Neutralization of polyalkalene carbonate polyols for polyurethane prepolymer synthesis Download PDFInfo
- Publication number
- AU605240B2 AU605240B2 AU11498/88A AU1149888A AU605240B2 AU 605240 B2 AU605240 B2 AU 605240B2 AU 11498/88 A AU11498/88 A AU 11498/88A AU 1149888 A AU1149888 A AU 1149888A AU 605240 B2 AU605240 B2 AU 605240B2
- Authority
- AU
- Australia
- Prior art keywords
- acid
- prepolymer
- stirring
- polyalkylene carbonate
- carbonate polyol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Ceased
Links
- 229920005862 polyol Polymers 0.000 title claims description 23
- -1 carbonate polyols Chemical class 0.000 title claims description 11
- 229920001730 Moisture cure polyurethane Polymers 0.000 title claims description 5
- 238000006386 neutralization reaction Methods 0.000 title description 9
- 230000015572 biosynthetic process Effects 0.000 title description 4
- 238000003786 synthesis reaction Methods 0.000 title description 4
- 239000002253 acid Substances 0.000 claims description 40
- 238000000034 method Methods 0.000 claims description 25
- 229920001281 polyalkylene Polymers 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 9
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 7
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 6
- 229920001228 polyisocyanate Polymers 0.000 claims description 6
- 239000005056 polyisocyanate Substances 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 3
- 239000003085 diluting agent Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims 2
- 150000003077 polyols Chemical class 0.000 description 13
- 239000004814 polyurethane Substances 0.000 description 10
- 229920002635 polyurethane Polymers 0.000 description 10
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 7
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 6
- 239000006260 foam Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000001879 gelation Methods 0.000 description 4
- 241000894007 species Species 0.000 description 4
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 238000013459 approach Methods 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 238000005829 trimerization reaction Methods 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010237 hybrid technique Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000008259 solid foam Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000004072 triols Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/089—Reaction retarding agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/41—Compounds containing sulfur bound to oxygen
- C08K5/42—Sulfonic acids; Derivatives thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polyesters Or Polycarbonates (AREA)
Description
AUSIRATLIA
Patents Act
P
Class It. Class Application Number: Lodged: Complete Specification Lodged: Accepted: Published: Priority This docuiment contains the Related Art: amendmeis made unduir Section 49 and is corr-ect for, printing.
APPLICANT'S R1EKWXi: 34,982-F Nae(s) of Applikant(s): The Dow Chemical Coup~any Address(es) of Applicant(s): 2030 Dow Center, Abbott Road, Midland, Michigan 48640, UNITED STATES OF AMERICA.
Address for Service is: PHLLIPS (iovNE a FITZPAmRCK Patent and Trade Mark Att6rnieys; 4 367 Collins Street Melbourne 3000 AUSTRALIA Complete Specification for the invention entitled: NEUTRALIZATION OF POLYALKALEIE CARBOIATM POLY=OL FM PLYURETflANE Our Ref 84105 POF Col!e: 1037/1037 The follov~ng statement is a full description of this invention, including the best method of performing it known to applicant(s): 6003q/ 1 1 i-n t i; i -1A- NEUTRALIZATION OF POLYALKYLENE CARBONATE FOLYOLS FOR POLYURETHANE PREPOLYMER SYNTHESIS Polyurethanes come to mind first when one thinks of foam products, and indeed polyurethanes dominate the solid foam market. Such foams may be either rigid or flexible, depending on how the process of manufacture takes place. In fact, polyurethane systems allow enormous variations in the po.lymerization and fabrication processes; it is thi" complexity which keeps the urethane area a fertile field for development and expansion.
Like many macromolecules, polyurethanes are a general class of materials which can be prepared via many different routes, at least in principle. However, industrial practicalities dictate a preferred approach based on, for example, feedstock availability and ease of processing. For example, ordinary condensation polymerization of bischloroformates with diamines will yield polyurethanes, but the universal large scale practice calls for condensation of diisocyanates with diols. (More generally, the common synthesis involves diisocyanates and polyols, wherein the diol is a special case, where triol species produce 34,982-F -1A i rl" -2crosslinking). A typical instance might have 2,4toluene diisocyanate (TDI) reacting with 1,4butanediol. In any case, the practical problems show up not at the level of individual chemical molecules but rather with the physical production and molding steps.
Polyurethanes are notoriously defiant regarding fabrication. The production -of a good, useful foam object involves precise control over the size and distribution of the hollow voids, or cells in the product. An open cell foam would make a poor life preserver while a closed cell foam would make a poor sponge. Volumes have been written on the problems associated with polyurethane processing, and the subject is generally beyond the scope of this discussion, except as relates to prepolymer stabilization.
Most polyurethanes cannot simply be made into a melt and injected into a mold in the way that polyethylene normally perform. One viable method is the "one shot" approach, whereby all the reactants are combined simultaneously with injection into the mold.
The alternative process calls for controlled synthesis of a prepolymer, a short chain polyurethane intermediate. The use of the intermediate provides a polyurethane which has generally better properties. The prepolymer method is generally more forgiving than the one shot approach, and hybrid techniques are possible, but the present art still has much room for improvements. This patent addresses the practical problem of prepolymer stability.
C-~I-IIPICYIY "7 -2a- According to the present invention there is provided a process for preparing a stabilized polyurethane prepolymer which comprises reacting a polyalkylene carbonate polyol with a polyisocyanate, characterized by mixing a strong acid with the polyalkylene carbonate polyol before or after the polyalkylene carbonate polyol is reacted with the polyisocyanate, the amount of the acid being sufficient to provide a negative controlled polymerization rate.
'i t tIo7 t I ioo s I m i -3- In particular, the present invention provides for treatment of polyols: this process involves the treatment of polyalkylene carbonate polyols, leading to more stable prepolymers and improved urethane products.
Polyalkylene carbonate (PAC) polyols may be made by a base-catalyzed reaction, and some catalyst remains in the product PAC. Accordingly, the prior art has depended on residual acid spe-cies, HC1, in the TDI to neutralize the residual base species in the polyol. Where necessary, it is-possible-to add an acid chloride to the TD1 (invariably benzoyl chloride) to provide for the neutralization; but the limitation on the prior art is that benzoyl chloride simply does not stabilize PAC prepolymers even when added in large excess. Benzoyl chloride may prevent a runaway exothermic reaction, but even so, it is just as objectionable as HC1 for many applications because residual chloride ions remain in the product. Even further, benzoyl chloride does not provide a st .ble prepolymer. The present invention produces stable PAC prepolymers with dual advantages of longer storage times (before fabrication) and longer gel times (during fabrication). Thus, premature curing does not occur, and the molded products have better physical properties, environmental resistance, etc.
The PAC polyol is typically a diol with an equivalent weight of about 250 to 2000, although triols 30 are available. Addition of a strong acid to the PAC polyol neutralizes the residual base catalyst, preventing side reactions, including trimerization of the TDI.
Specifically, the PAC polyul requires initial characterization with respect to its "CPR" count.
341982-F -3- 1' i" -4- "CPR" represents the phrase "controlled polymerization rate," signifying the amount of residual base in the prepolymer. CPR determination protocol calls for 30 g of PAC in 100 ml of methanol to be titrated with 0.01 N HC1, where the ten times the acid volume is equal to the CPR value. See "Urethane Polyether Prepolymers and Foams: Influence of Chemical and Physical variables on Reaction Behavior" by Schotten, Schuhmann, and TenHoor, in J. Chem. Eng. Data, Vol. 5, No. 3, July 1960. The key is to achieve a negative CPR value by addition of the strong acid. But a CPR value below -100 would be unnecessary, possibly even counterproductive and detrimental to the product.
1 The strong acids used here include methanesulfonic acid (MSA) and para-toluenesulfonic acid (PTSA). Certainly many other strong acids will also work, but each acid type should be tested experimentally, not to verify its ability to clean up the PAC polyol, but rather to determine whether unwanted side reactions also occur. For example, as suggested earlier, HC1 has been found to be an undesirable acid. But it is equally clear that virtually any organosulfonic acid will perform satisfactorily.
Furthermore, some acids react directly with TDI, H 2
SO
4 AND PTSA; so it is necessary to treat the PAC polyol with the acid prior to its reaction with a polyisocyanate.
The process involves mixing an acid with a selected polyol, more particularly with PAC, either before or after it is reacted with a polyisocyanate to form a prepolymer. The mixing procedure s best 34,982-F -4carried out at 60°F (15 0 C) to 95 0 F in a closed container. The acid is added to the PAC with stirring.
The acid is stirred into the PAC using, for laboratory amounts, a stirring device, to mix acid. The amount of acid is quite small; as an example, for one liter of PAC, acid is added with stirring in an effective amount of just a few ppm, or only a few drops. Since only a small amount of acid is needed, a neutral diluent (preferably the PAC polyol itself) is added to the 'I0 acid, perhaps 10 to 50 to one of acid. The acid is added over time with stirring. If the residual base species in the PAC is known before treatment, the amount of acid can be calculated. On'the other hand, acid can be ratably added to achieve base neutralization over time to avoid excessive over dosing. Therefore, the preferred procedure is adding acid while stirring the PAC until the requisite neutralization is accomplished. This extent of acid addition varies primarily with the degree of PAC neutralization. Should insufficient acid be added, the step is repeated until a negative CPR value is obtained.
The following examples and comparative run are provided to illustrate the invention but are not intended to limit the score thereof.
Comoarative Run A This comparative run shows the inefficacy of benzoyl chloride as a stabilizer. A PAC polyol was reacted with toluene diisocyana'e to form a prepolymer having an isocyanate content of 5 percent. The prepolymer CPR values were found according to the procedure nentioned above. Viscosity of the prepolymer 34,982-F -6after treatment is given in centipoises, as measured with a Brookfield Viscometer Model RVTD. This machine is.rotational viscometer containing various spindles, previously calibrated by the manufacturer. The spindle is placed in the solution to be analyzed and rotated.
The viscosity is calculated by multiplying the RPM by the appropriate spindle calibration factor.
TABLE I 0 Prepolymer Prepolymer Viscosity, Time Before CPR cp (Pats) Gelation 1.76 instantaneous 1.40 74,200 (74.2) 1 hour 0.99 40,400 (40.4) 1 day 0.006 33,000 (33) 1 day -2.01 27,000 (27) 1-2 days -4.98 24,000 (24) 1-2 days -7.95 29,800 (29.8) 1-2 days -13.89 41,200 (41.2) 1-2 days -31.35 37,000 (37) 1-2 days -61.41 26,800 (26.8) 1-2 days Various side reactions appear to have occurred, including trimerization of the isocyanate, resulting in gelation.
Example 1 In a second tes' described in Table II, PTSA Was used to treat a quantity of PAC. The treated PAC was then reacted with an excess of toluene diisocyanate to form a prepolymer containing 5 percent isocyanate groups. Measurements were taken after 24 hours at 80 0
C.
34,982-F -6- -7- TABLE II CPR of PAC PREoolymer Result 5.2 1.2 0.2 .0 ,gel1at ion gelation no gelation (still liquid) no gelatUiomn (still liquid) The first two runs evidence triruerization with the TDI, while the two runs at lower, CPR show stability of the pr6polymer made with a properly treat~d PAC, Examole 2 For a third test described in Table IIU, more quantitative data was obtained by measuring AONCO lo.ss (a wdeight percent of the prepolymer). The percentage, Value is found by carrying out a dibu'tylamine reaction, followed by back titratin with HCl, Measurements were taken after 24 hours at 80 0
C.
TABLE III CPR of PAC Acid 1.7 Benzoyl chloride
PTSA
MS A Prepolymer NCO Lost a-elation 0,0 0.01 Treatment or neutralization of the polyOl In the lat.ter two cases was sufficient to stop virtually any trimerization of the prepolymer.
341,98 2-F -7- -8- As shown from the foregoing tables, PAC polyol neutralization is accomplished to obtain a more useful prepolymer. While variations in the present process may be incorporated, the scope of the present disclosure is determined by the claims which follow.
34,982-F
Claims (10)
1. A process for preparing a stabilized polyurethane prepolymer which comprises reacting a polyalkylene carbonate polyol with a polyisocyanate, characterized by mixing a strong acid with the polyalkylene carbonate polyol before or after the polyalkylene carbonate polyol is reacted with the polyisocyanate, the amount of the acid being sufficient to provide a negative controlled polymerization rate.
2. A process as claimed in claim 1 wherein the acid is an organosulfonic acid.
3. A process as claimed in claim 1 or claim 2 wherein the addition of acid proceeds until a negative controlled S* polymerization rate is obtained. S 4. A process as claimed in any one of claims 1 to 3 T wherein the acid is para-toluenesulfonic acid or methanesulfonic acid. A process as claimed in any one of claims 1 to 4 S wherein the acid is rateably added with stirring.
6. A process as claimed in any one of claims 1 to wherein the step of adding acid is repeated until a negative controlled polymerization rate is measured for the polyalkylene carbonate polyol.
7. A process as claimed in claim 5 or claim 6 wherein the stirring is conducted at ambient temperature,
8. A process as claimed in any one of claims 5 to 7 S wherein the stirring is accomplished with a stirring means.
9. A process as claimed in any one of claims 5 to 8 wherein stirring is done in a closed container. A process as claimed in any one of claims I to 9 wherein the acid is mixed with a diluent before addition to the polyalkylene carbonate polyol.
11. A process as claimed in any one of claims 1 to wherein the acid is added before preparation of the prepolymer, i2. A process as claimed in any one o£ claims 1 to wherein the acid is added after preparation of the prepolymer.
13. A stabilized polyurethane prepolymer made by the practice of the process as claimed in any one of claims 1 to 12 -1 1~ 4
14. A process as claimed in claim 1 substantially as hev~zeinbefore described with reference to any one of the examples. DATED; 2 October 1990 0 0 4 a 4 PHILLIPS ORMONDE &x FITZPATRIC Patent Attorneys for: THE DOW CHEMICAL COMPANY 1762U 4*44 4 *444 4444 4 *4 *4 4 44~ MW 0 VL
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US1495487A | 1987-02-17 | 1987-02-17 | |
| US014954 | 1987-02-17 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| AU1149888A AU1149888A (en) | 1988-08-18 |
| AU605240B2 true AU605240B2 (en) | 1991-01-10 |
Family
ID=21768761
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| AU11498/88A Ceased AU605240B2 (en) | 1987-02-17 | 1988-02-10 | Neutralization of polyalkalene carbonate polyols for polyurethane prepolymer synthesis |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0363360A4 (en) |
| JP (1) | JPH02501830A (en) |
| AU (1) | AU605240B2 (en) |
| BR (1) | BR8807361A (en) |
| CA (1) | CA1320772C (en) |
| WO (1) | WO1988006150A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2058048T3 (en) * | 1992-03-24 | 1999-06-16 | Dow Chemical Co | NEW FINISHING PROCEDURE FOR HYDROXY-FUNCTIONAL POLYETERS. |
| TWI761404B (en) * | 2016-12-19 | 2022-04-21 | 德商科思創德意志股份有限公司 | Process for producing (cyclo) aliphatic polycarbonate polyols having low reactivity |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3770793A (en) * | 1970-05-15 | 1973-11-06 | American Cyanamid Co | Aminium and dimonium salts used as polymerization inhibitors of diallyl digylcol carbonate |
| US4448727A (en) * | 1976-03-22 | 1984-05-15 | General Electric Company | Color-stabilized halobisphenolethylene polycarbonates |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU536979B2 (en) * | 1982-04-26 | 1984-05-31 | Ppg Industries, Inc. | Polyol(allyl carbonate) composition |
| DE3231397A1 (en) * | 1982-08-24 | 1984-03-01 | Bayer Ag, 5090 Leverkusen | USE OF CARBONYL COMPOUNDS AND / OR HETEROANALOGIC CARBONYL COMPOUNDS AS A STABILIZING AGENT FOR SOLUTIONS CONTAINING PYROCARCOURED ACYLEDIUM CYLESTER AND POLYISUBYANITATE-ZONATE COMPOUNDS |
| US4528364A (en) * | 1984-04-19 | 1985-07-09 | The Dow Chemical Company | Removal of alkaline catalysts from polyether polyols and polyalkylene carbonate polyols |
| US4814428A (en) * | 1987-06-04 | 1989-03-21 | General Electric Company | Method of increasing the thermal stability of cyclic carbonate oligomers |
-
1988
- 1988-02-01 JP JP63501715A patent/JPH02501830A/en active Pending
- 1988-02-01 WO PCT/US1988/000285 patent/WO1988006150A1/en not_active Ceased
- 1988-02-01 BR BR888807361A patent/BR8807361A/en not_active Application Discontinuation
- 1988-02-01 EP EP19880901720 patent/EP0363360A4/en not_active Withdrawn
- 1988-02-05 CA CA000558306A patent/CA1320772C/en not_active Expired - Fee Related
- 1988-02-10 AU AU11498/88A patent/AU605240B2/en not_active Ceased
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3770793A (en) * | 1970-05-15 | 1973-11-06 | American Cyanamid Co | Aminium and dimonium salts used as polymerization inhibitors of diallyl digylcol carbonate |
| US4448727A (en) * | 1976-03-22 | 1984-05-15 | General Electric Company | Color-stabilized halobisphenolethylene polycarbonates |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0363360A1 (en) | 1990-04-18 |
| AU1149888A (en) | 1988-08-18 |
| CA1320772C (en) | 1993-07-27 |
| EP0363360A4 (en) | 1990-06-27 |
| JPH02501830A (en) | 1990-06-21 |
| WO1988006150A1 (en) | 1988-08-25 |
| BR8807361A (en) | 1990-03-01 |
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