JPH0469174B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to the production of polyols containing other polymers. The polyols of the present invention can be referred to as polymer polyols. Polyurethanes constitute a broad group of polymeric materials that have a wide range of physical properties. The polymer is produced by the interaction of a polyfunctional isocyanate with a polyfunctional chemical having active hydrogen within its structure, such as a polyester, polyether or a mixture of two or more such materials. . Conventionally, the materials used contain two or more hydroxyl groups and are therefore generally defined as polyols. It is known in the art that the physical properties of the resulting polyurethane composition can be improved to some extent by adding a high molecular weight polymer to the polyurethane composition. Significant efforts have been made to incorporate polymers into such polyurethane compositions. For example, U.S. Pat.
No. 3,383,351 discloses the in situ polymerization of ethylenically unsaturated monomers in the presence of the polyol component of a polyurethane composition. Prior art techniques include polymerizing ethylenically unsaturated monomers in the presence of an isocyanate-terminated prepolymer to form an isocyanate-terminated polymer prepolymer. This technology is described in U.S. Patent No.
No. 3,968,089 and the preparation of graft copolymer dispersions by in situ polymerization of vinyl monomers in the presence of polyols containing unsaturated bonds is also described, for example, in US Pat. No. 3,953,393. The present invention provides a method of forming polymers to achieve degrees of freedom not found in the prior art. According to the present invention, (a) an ethylenically unsaturated monomer is polymerized into a low molecular weight liquid polymer using an anionic catalyst in a selected medium; and (b) in a polyol different from the medium of step (a). A process for producing a polymer polyol is obtained, characterized in that the polymer from step (a) is mixed in step (a), and (c) the polymer is crosslinked in the polyol. The invention disclosed herein involves polymerizing monomers in a selected medium, stopping the polymerization at a selected time, and
This relatively low molecular weight polymer is then dispersed in a polyol and the polymer is then crosslinked to the desired level. By this method the microstructure of the initial polymer can be controlled by known techniques, including judicious selection of the medium along with the selection of initiators for the first stage polymerization. This pre-produced low molecular weight polymer is then
It is dispersed in a polyol and crosslinked to an appropriate level while retaining its internal structural properties.
Prior art techniques for polymerizing monomers in polyols are unable to incorporate such treatments into the polymer portion of the polymer polyol. Monomers useful in the practice of this invention are polymerizable ethylenically unsaturated monomers containing at least one polymerizable ethylene group. The monomers may be used singly to produce homopolymers/polyols or in combination to produce copolymers/polyols. These monomers are known and include butadiene, isoprene, 1,4-pentadiene, 1,
Hydrocarbon monomers such as 6-hexadiene, 1,7-octadiene, styrene, α-methylstyrene, 2,4-dimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, phenylstyrene, cyclohexylstyrene and benzylstyrene; chloro Styrene, 2,5-dichlorostyrene, bromostyrene, fluorostyrene, trifluoromethylstyrene, iodostyrene, cyanostyrene nitrostyrene, N,N-
Substituted styrenes such as dimethylaminostyrene, p-vinyldiphenyl sulfide and p-vinylphenyl phenyl oxide; methyl acrylate, methyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, isopropyl methacrylate, octyl methacrylate,
Methacrylonitrile, methyl α-chloroacrylate, ethyl α-ethoxy acrylate, methyl α-acetaminoacrylate, butyl acrylate, 2-ethylhexyl acrylate,
Acrylic and substituted acrylic monomers such as phenyl acrylate, phenyl methacrylate and α-chloroacrylonitrile; vinyl acetate, vinyl chloroacetate, vinyl butyrate, isopropenyl acetate, vinyl formate, vinyl acrylate, vinyl methacrylate, vinyl methoxy acetate, Vinyl benzoate, vinyl naphthalene, vinyl bromide, vinyl fluoride, vinylidene bromide, 1-chloro-1-fluoro-ethylene, vinylidene fluoride, vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, vinyl butyl ether, vinyl 2-ethylhexyl ether , vinyl phenyl ether, vinyl 2-methoxyethyl ether, methoxybutadiene, vinyl 2-butoxyethyl ether, 3,4-dihydro-1,2
- vinyl esters and vinyl ethers such as pyran, 2-butoxy-2'-vinyloxy diethyl ether, vinyl 2-ethyl mercaptoethyl ether, vinyl methyl ketone, vinyl ethyl ketone and vinyl phenyl ketone; dimethyl fumarate, dimethyl maleate , monomethyl itaconate, dimethylaminoethyl methacrylate, glycidyl acrylate, dichlorobutadiene, vinylpyridine, and hydroxyethyl methacrylate. The compounds described above are illustrative and not limiting of suitable monomers for use in the present invention. Preferred ethylenically unsaturated monomers for the practice of this invention include hydrocarbon monomers such as butadiene, isoprene, styrene and alpha-methylstyrene and isocyanate groups such as methyl acrylate, methyl methacrylate, hydroxyethyl methacrylate, acrylonitrile and methacrylonitrile. Examples include acrylic monomers and substituted acrylic monomers that do not react with. The first stage polymerization or copolymerization of these monomers to produce low molecular weight liquids is accomplished by a variety of known techniques. These low molecular weight polymers should generally have a molecular weight of 1800-8000. One skilled in the art can select the polymerization method to obtain the desired microstructure for the polymer. Free radical and cationic catalysts give highly branched polymers, while anionic and Zieglev-Natta catalysts give products with a linear structure. Preferred low molecular weight polymers are obtained by anionic polymerization or copolymerization of ethylenically unsaturated monomers, most preferably butadiene. Such polymers include Revertex Ltd., Temple Fields, Harlow, Essex, UK;
LITHENE liquid polymer of butadiene manufactured by Harlow Essex, Great Britain). These preferred LITHENEs are prepared by anionic polymerization of butadiene, as described in the product data. An organolithium catalyst is used in a solvent. Although toluene is listed as a common solvent, it is only one of many solvents that can be used. Butadiene monomer (CH ₂ = CH−
Anionic polymerization of CH=CH ₂ ) gives three different types of structures.

【formula】

【formula】

1,4- 1,2- Cyclization By adjusting these structures by known methods, the overall microstructure of the polymer can be adjusted. For this reason, the person skilled in the art can then select the type of polymer that he wishes to further crosslink in the polyol. Other types of low molecular weight liquid polymers preferred for crosslinking in polyols include those terminated with hydroxy groups having internal unsaturation and having molecular weights from 1800 to 8000. for example,
Such polybutadiene and butadiene-ethylene copolymers are available from ARCO chemical CO., a division of Atlantic Richfield, Inc.
Poly bd Liquid Resine (trade name) manufactured by Richfield Co., Ltd. has the following published structure. homopolymer (In the formula, n is 50) Copolymer HO [(---CH ₂ -CH=CH-CH ₂ ) _a - (CH ₂ -CH ₂ ) _b ]
--- _o OH where a is 0.75, b is 0.25 and n is 54 These polymers are proposed to be used as suitable components to react with polyisocyanates to form polyurethanes. There is. In the present invention, these hydroxyl-terminated polymers are suitable for crosslinking in polyols, just like the non-hydroxyl-terminated polymers mentioned above. The same group of monomers that are useful for polymerizing non-hydroxy-terminated polymers are useful for polymerizing to obtain hydroxy-terminated polymers. Methods for producing these substances are known. Polyether polyol components useful in the preparation of polymer polyol compositions have a functionality of 2 to 6 and have a functionality of 2,000 to 10,000, preferably 2,000
Mention may be made of polyols with a molecular weight of ~7000. These polyether polyols include trimethylolpropane, glycerol, 1,2,6-
Well-known processes involving the reaction of polyvalent initiators such as hexanetriol, sorbitol or pentaerythritol with alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, or mixtures of ethylene oxide and propylene oxide and/or butylene oxide. Manufactured by. This reaction is carried out by well known methods using an alkoxylation catalyst, typically an alkali metal hydroxide, such as potassium hydroxide. The alkoxylation reaction is continued until the product reaches the desired molecular weight. Particularly preferred polyether polyols are polyether triols. Preferred polyether diols are, for example, polypropylene glycols or mixed polypropylene glycol/polyethylene glycol copolymers with a molecular weight of 2000 to 5000. These materials are produced by reacting ethylene oxide, propylene oxide or butylene oxide either sequentially or in admixture with initiators such as ethylene glycol, propylene glycol or butylene glycol. Another preferred polyol is one produced by impregnating the inside of a polyol with an epoxy resin. These polyols are described, for example, in US Pat. No. 4,316,991. The polyether polyol and the pre-prepared low molecular weight liquid polymer are mixed or dispersed together and then further crosslinked, for example by a catalyst such as a free radical catalyst or an azo compound. This crosslinking technique is generally performed under the following conditions. Usually, crosslinking of the pre-prepared liquid polymer takes place at a temperature of 100-150°C, preferably 110-140°C. Crosslinking may proceed under atmospheric or sub-atmospheric conditions. The following non-limiting examples illustrate the implementation of the invention. Example 1 Into a three-necked flask equipped with a stirrer, thermometer, condenser, and nitrogen supply port, a sample having a molecular weight of 5500
Propylene oxide/ethylene oxide (PO/EO) adduct of glycerol (THANOL SF-5505)
320 g, 80 g of butadiene liquid polymer having a molecular weight of 5000 (LITHENE N4-5000) and 4.0 g of 2,5-dimethyl-2,5-di(t-butylperoxy)hexane (LUPERSOL 101: trade name) were charged. The reaction mixture was heated at 125-135° C. for 5 hours while maintaining a nitrogen purge. The product was then stabilized with 1.3 g of 2,6-di-t-butyl-4-sec-butylphenol (ISONOX 132). The final product was a white, opaque, viscous liquid with the following characteristics: This polymer polyol was stable in glass for 3 months. Acid number (mg KOH/g) 0.015 Hydroxyl number (mg KOH/g) 32.6 Moisture (wt%) 0.01 PH (10:6 isopropanol/water) 6.8 Viscosity at 25°C (cps) 3720 The physical mixture of the above reactants is Initial viscosity is 25℃
It was 1800 cps and separated into phases within a few days. Example 2 This example shows the production according to Example 1 in a scaled-up manner. THANOL SF for 30 reactors
−5505 polyol 3.63Kg, LITHENE N4−5000
0.91Kg and LUPERSOL 101 45.4g were input.
The reactor was then evacuated and purged with prepurified nitrogen. It was then heated at 128-130°C for 3 hours. The reaction was monitored by measuring the viscosity every hour. The results are shown below. Time (hours) Viscosity 25°C (cps) 0 1860 1 2100 2 2100 3 2340 The product was then stabilized with 6.8 g of di-t-butyl-p-cresol. According to GPC, the product was 10% of the polymer with 2-3 times the molecular weight of the starting material on the chromatogram. Example 3 This example describes the steps in the production of RIM elastomer.
Figure 2 illustrates the use of the polybutadiene polymer polyol of Example 2. Additionally, this example also demonstrates the improved hydrolytic stability and heat sag properties of elastomers made using these materials. These elastomers were manufactured using an Accuratio machine.

[Table] 1: PO/EO adduct of glycerin with a molecular weight of 5500:
Texaco Chemical Company 2: Obtained from Example 1 3: 80:20 EO/PO diol with molecular weight 11000:
BASF (Wyandotte) 4: Dimethylaminoethanol: Texaco Chemical Co. 5: SUL-4 (product name): Witco Chemical Co. 6: Thioorganotin compound: Witco Chemical Co. 7: Liquid MDI: Upjohn Chemical Co. 8: Isocyanate-rich pseudoprepolymer:
THANATE L-55-O (trade name): Texaco Chemical Company Example 4 This example demonstrates the use of a polybutadiene polymer polyol (prepared in Example 1) in the production of a high resiliency (HR) foam. Furthermore, this example shows that the foam has good properties throughout. The blending ratio, manufacturing details, and characteristics are shown below. Blending ratio, weight part A THANOL SF-5505 60 Polybutadiene polymer polyol 40 Water 2.8 Q2-5043 Silicone ¹ 2.0 THANCAT TD-33 ² 0.25 NIAX A-1 ³ 0.25 THANCAT DM-70 ⁴ 0.25 Dibutyltin dilaurate 0.01 80:20TDI/PAPI ⁵ 35.1 Isocyanate Index 1.02 Manufacturing Details Cream Time (sec) 6 Rise Time (sec) 120 Gel Time (sec) 195 Characteristic Density (g/ ^cm3 ) 0.038 Tensile Strength (MPa) 0.092 Elongation (%) 119 Tear Strength (N/m) 2.28 Compression set 50% 21.1 95% 18.2 Wet aging (5 hours at 121°C) Compression set (%) 22.1 CLD loss, 50% ⁶ 9.99 1: Dow Corning
Corp. 2: 33% triethylene diamine in propylene glycol: Texaco Chemical Co. 3: Bis-dimethylaminoethyl ether: Union Carbide Chemical Co. 4: 70% dimorpholino diethyl ether/30%
N,N'-dimethylpiperazine: Texaco
Chemical Co. 5: High molecular weight isocyanate with functionality of 2.7: Mobay Chemical Co.
Product 6: Compressive Load Deflection Example 5 This example demonstrates the polymerization of a hydroxyl terminated polybutadiene liquid polymer in THANCL SF-5505 polyol. THANOL was added to a three-necked flask equipped with a stirrer, thermometer, condenser, and nitrogen inlet.
SF-5505 polyol 400g, hydroxy-terminated polybutadiene liquid polymer [poly bd
R-45M (trade name), ARCO Chemical Co.] 100g and
5.0 g of LUPERSOL 101 (trade name) was added. At this point, the reaction had a viscosity of 1340 cps at 25°C. The reaction mixture was heated at 128-135° C. for 4.75 hours while maintaining a nitrogen purge. The reaction mixture was then cooled and stabilized with 0.5 g of ISONOX 132. The final product was a white, opaque, viscous liquid with the following characteristics: Acid number (mg KOH/g) 0.13 Hydroxyl number (mg KOH/g) 36.6 Moisture (wt%) 0.01 Viscosity at 25°C (cps) 6300 Peroxide (ppm) 1.95 Example 6 Stirrer, thermometer, condenser and nitrogen In a three-necked flask equipped with a feed port, add a propylene oxide/ethylene oxide/diglycidyl ether adduct of glycerol bisphenol A with a molecular weight of 3500.
400 g, 100 g of butadiene liquid polymer with a molecular weight of 5000 (LITHENE N4 5000) and
5.0g of LUPERSOL101 was added. The reaction mixture was heated at 125-135° C. for 3 hours while maintaining a nitrogen purge. The product was then stabilized with 0.75 g of di-t-butyl-p-cresol. The final product was a white, opaque, viscous liquid with the following characteristics: Hydroxyl Number (mg KOH/g) 42.3 Viscosity, 25°C (cps) 1538 The physical mixture of the above reactants has a viscosity of 1275 cps at 25°C.
It had a viscosity of Example 7 This example demonstrates the use of the polymer polyol of Example 9 in the production of flexible foams. Furthermore, this example shows that glycerol propylene oxide/ethylene oxide (THANOL F-
3016) and the base polyol of Example 6, foams made from this polyol show improved load carrying capacity.
Load carrying capacity was measured using a Chatillon gauge (indentation: 33%). The blending ratio, manufacturing details, and foam characteristics are shown below.

[Table] 1: Union Carbide Co. product 2: Triethylenediamine in propylene glycol: Texaco Chemical Co. product 3: Manual model L manufactured by John Chatillon and Sons・I・C (Manual
Model LIC) Compression testing machine

Claims (1)

Claims: 1. (a) polymerization of ethylenically unsaturated monomers into a low molecular weight liquid polymer using an anionic catalyst in a selected medium; (b) a polyol different from the medium of step (a); process inside
A method for producing a polymer polyol, comprising: (a) mixing the polymers; and (c) crosslinking the polymers in the polyol. 2 The molecular weight of the polymer from step (a) is 1800 to
8000, the method of claim 1. 3. The method according to claim 2, wherein the polyol in step (b) has a molecular weight in the range of 2,000 to 7,000.