JPS59168021A - Manufacture of composition containing free isocyanate group or free hydroxy group for making polyisocyanate - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the production of polyol or incyanate prepolymers containing other polymers.

It also relates to the production of polyurethanes obtainable from such compositions. The polyols of the invention may also be referred to below as polymer polyols. Incyanate compositions may also be referred to below as polymer prepolymers.

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, a polyether, or a mixture of two or more such materials. be done. Conventionally, the materials used contain two or more hydroxyl groups and are therefore generally defined as polyols. In the preparation of flexible polyurethane foams, the quasi-prepolymer method (quaai-pr
It may be convenient to use a method known as the polymer method. In a second step, the pseudoprepolymer is then mixed with the remainder of the polyether polyol along with blowing agent and catalyst to produce polyurethane foam. This type of pseudogrepolymer with excess incyanate is referred to below as incyanate-terminated prepolymer.

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, US Patent Application 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, in the presence of incyanate-terminated prepolymers,
Techniques include polymerizing ethylenically unsaturated monomers to form in7anate-terminated polymer prepolymers.

This technique is described in U.S. Patent Application No. 3,968.08.9
It's in the issue. 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 Patent Application No. 3,953,393.

The present invention provides a method of forming polymers to achieve degrees of freedom not found in the prior art.

The present invention relates to a method for producing a polyurethane-forming composition comprising an ethylenically unsaturated monomer, a resulting crosslinked polymer, and an active ingredient containing free hydroxy groups or free isocyanate groups. A composition for forming a polyurethane, characterized in that it is mixed with a liquid polymer obtained by polymerizing an ethylenically unsaturated monomer in a medium different from the above, and the liquid polymer is crosslinked in the presence of the above-mentioned active ingredient. Regarding the manufacturing method.

The invention also relates to the use of the resulting composition in forming polyurethanes by reacting the composition with polyisocyanates or polyols, respectively.

The invention disclosed herein involves polymerizing the monomers in a selected medium, terminating the polymerization at a selected point, and then adding this relatively low molecular weight polymer to an active ingredient (e.g., a polyol or an incyanate-terminated polymer). prepolymer) and subsequent crosslinking of the polymer 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 the active ingredient and crosslinked to an appropriate level while retaining its internal structural properties. Prior art methods of polymerizing monomers in the active ingredient do not allow for the incorporation of such treatments into the polymer portion of the polymer polyol, polymer or prepolymer.

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 or in combination to produce copolymers.

These monomers are known and include butadiene, isoprene, 1,4-pentadiene, 1°6-hexadiene, 1,7-octadiene, styrene, α-methylstyrene, 2,4-dimethylstyrene, ethylstyrene, Hydrocarbon monomers such as improvylstyrene, butylstyrene, phenylstyrene, cyclohexylstyrene and benzylstyrene; chlorostyrene, 2,5-dichlorostyrene, bromostyrene, fluorostyrene.

Nitrostyrene, N,N-dimethylaminostyrene, p
- substituted styrenes such as vinyldiphenylsulfy FJ,, p-vinylphenylphenyl oxide;
Methyl acrylate, methyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, isopropyl methacrylate, octyl methacrylate, trimethacrylate, methyl-α-chloroacrylate,
Acrylic and substituted acrylic monomers such as ethyl Oα-ethoxy acrylate, methyl α-acetaminoacrylate, butyl acrylate, 2-ethylhexyl acrylate, phenyl acrylate, phenyl methacrylate-1, and α-chloroacrylonitrile; vinyl acetate, and vinyl chloroacetate, vinyl butyrate, impropenyl acetate, vinyl formate, vinyl acrylate, vinyl methacrylate, vinyl methoxy acetate, vinyl benzoate, vinylnaphthalene, vinyl promide, vinyl formate, vinylidene promide, ■-chloro-1-fluoro Ethylene, vinylidenepromide, vinyl, methyl ether, vinyl ethyl ether, vinyl ethyl 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-bilane, 2-butoxy-2'
- vinyl esters and vinyl ethers such as vinyloxydiethyl ether, vinyl 2-ethyl mercaptoethyl ether vinyl methyl ketone, vinyl ethyl ketone and vinyl erectone; dimethyl fumarate, dimethyl maleate, monomethyl itaconate, dimethylaminoethyl methacrylate, glycidyl Examples include 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 generally have a molecular weight of 1
Must be between 800 and 8000. One skilled in the art can select the polymerization method to obtain the desired microstructure for the polymer. Free radical and cationic catalysis yield highly branched polymers, whereas anionic and zieglev-Natta
) The catalyst gives a product with a cylindrical structure.

Preferred low molecular weight polymers are obtained by anionic polymerization or copolymerization of ethylenically unsaturated monomers, most preferably butadiene. One such polymer is Essex, UK.

Revertex Ltd, Templefield, Barlow
Fields, HarlowEssex, Gr.
Butadiene LITH manufactured by EatEr1tain)
Examples include BNE (trade name) liquid polymer.

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. Butadienmo/
Anionic polymerization of mer (OH2=C!HOH=0Hz) results in three different types of structures.

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 active ingredient.

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 between zsoo and 5ooo. For example, such polybutadiene and butadiene-ethylene copolymers are available from AROOchemical Co., a division of Atlantic-Ritchfield Corporation, div.
iaion of Atlantic-Rlehfi
Poly-B-D liquid resin (
Polybd Liquld Re5ine (trade name) is mentioned, and has the following published structure.

Homopolymers (where n is equal to 50) Copolymers (wherein a is 0.75, b is 0.25 and n is 54) These polymers are reacted with polyincyanates to form polyurethanes. It is proposed to be used as a suitable ingredient in

In the present invention, these hydroxyl-terminated polymers are suitable for crosslinking in polyols, just like the non-hydroxyl-terminated polymers mentioned above.

A similar family 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.

In one embodiment of the invention, the incyanate i-terminated polyether-based prepolymer composition is formed by the reaction of an organic polyisocyanate and a polyether polyol component, the incyanate i-terminated polyether Polymerization of ethylenically unsaturated monomers takes place in situ in ether-based prepolymer compositions. The above reaction results in the formation of a super-Z riether-based prepolymer composition ix having terminal isocyanate groups by reacting with the hydroxy groups of one isocyanate-based evolyether polyol of the polyisocyanate. This isocyanate-terminated, polyether-based prepolymer composition has a very low number of hydroxyl groups, indicating that all available hydroxyl groups have been reacted with isocyanate groups. be.

Polyether polyol components useful in the production of polymer polyol compositions have a functionality of from 2 to 6 and from 2,000 to 10,000, preferably from 2,000 to 70.
000 molecular weight total 7000 reol. These polyether polyols are prepared by combining polyvalent initiators such as trimethylolpropane, glycerol, 1,2°6-hexandriol, norbitol or pentaerythritol with ethylene oxide, propylene oxide, butylene oxide,
or by well-known methods involving the reaction of alkoxyl oxides with mixtures of ethylene oxide and propylene oxide and/or butylene oxide! ll manufactured. 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.

A particularly preferred polyether polyol is polyether hakamashi triol.

Preferred polyether diols have a molecular weight of 200, for example.
polypropylene glycol or mixed polypropylene glycol/polyethylene glycol copolymer having a molecular weight of 0 to 5000. These substances are produced by reacting ethylene oxide, propylene oxide or petile oxide either sequentially or in mixtures with initiators such as ethylene glycol, propylene glycol or haftyl 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 U.S. Patent Application Box 4,316,9
It is described in No. 91.

Polyisocyanate components useful in preparing prepolymer compositions include incyanates having two or more isocyanate groups per molecule. Specific examples of such incyanates include ij, 2,
Toluene diisocyanates such as 4- and 2,6-isomers and mixtures thereof, 2,2'-12,4'-
and methylene bis(phenylinocyanate), such as the 4,5'-isomer, and mixtures thereof.

Other typical aromatic incyanates include 1゜5-
Mention may be made of isomers of naphthylene diincyanate, phenyl diincyanate, xylylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diincyanate methyl ester, methylene bis(cyclohex/ruincyanate) and the like, as well as mixtures thereof.

Mixtures of diisocyanates 5 and high molecular weight isocyanates may also be used; Examples of mixtures are described in US Pat. No. 3,362,979. Examples of incyanates commonly used in the production of polyurethane foam include toluene diisocyanate, and polymethylene polyphenyl polyisocyanates having a functionality of 2.1 to 30. Any of the diphenylmethane diisocyanates and various aliphatic isocyanates M or the above-mentioned in7anates used in the present invention may be used as appropriate in the production of the polyneedle-based prepolymer with all incyanate groups being terminal groups. I can do it.

When producing a prepolymer composition having incyanate groups as terminal groups and having a polyether as a backbone, polyincyanate and polyether polyol are mixed in such an amount that the amount of organic polyisocyanate used is in excess. The equivalent ratio of incyanate groups to hydroxy groups, usually known as the incyanate index, is generally sufficient from 25 to 2, with an incyanate index of 20 to 4 being preferred. Generally, organic polyisocyanates are prepared under an inert atmosphere at elevated reaction temperatures (e.g., 50-150°C), preferably about 100°C, until all hydroxy groups have been treated with incyanate groups to form a prepolymer composition.
react with a polyether polyol at a temperature of .

The active ingredient and the pre-prepared low molecular weight liquid polymer are mixed together or dispersed together and then further crosslinked, for example by means of a catalyst, such as a free radical catalyst or an azo compound. This crosslinking technique is generally carried out under the following conditions.

Typically, the crosslinking of pre-prepared liquid polymers is ioo
Occurs at a temperature of ~150<0>C, preferably 110-140<0>C. Crosslinking may proceed under atmospheric or sub-atmospheric conditions.

The invention will now be described in detail by way of non-limiting examples.

Example 1 This example demonstrates the preparation of a NOO-based composition of the present invention.

In a III three-bottle flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen inlet, the ethylene oxide/contaminated propylene adduct of gulyarol, molecular weight 5000, was added CT.
i (ANOL 5F-5505; trade name, Texaco Chemical Co.,
) ) 250 g, high molecular weight incyanate (PAP
I9oi:m Product name, Upjohn Co.
, )) 250 g, liquid polymer of butadiene (LI
THENEN4-50002 Trade name, Revertex Ltd. 55.59 and 2,5-dimethyl-,,5-di(t-butylperoxy)hexay (LUPERsOr, 101: Trade name, Penvalt) N-cidol part (Lucidol)
Div, , PennwaltCorp, ))
I put in 5.559. The reaction mixture was heated at 130-135° C. for 3 hours while maintaining a nitrogen purge. The product was then converted into 2,6-di-tert-butyl-4-5ee-butylpheno-# (15ONOX132:m product name, 8chenectady Chemical Co.
Cherical Co, ))] 0.5 ji
It was stabilized. The final product was a dark colored, viscous liquid with the following characteristics:

Incyanate Fuyu (meq/g) 2.8
3 equivalent 35
3.3 Viscosity 25℃ (cps) 1
This example demonstrates the use of the incyanate group-containing composition of Example 1 in the preparation of a wet cure adhesive.

Additionally, this example shows that the adhesive produced by this product compared to one prepared by reacting a mixture of THANOL 5F-5505 polymer and PAPI 901 isocyanate at 90°C for 3 hours. Indicates that the characteristics have been improved. The latter product contains incyanate containing iii: 3.25 me (p/g (equivalent weight: 30
7.6) and viscosity (25°C): 5600 cps.

To 100.9 g of the product of Example 1 were added 20.9 g of DAROOG-60 carbon black and 2.5 g of 0ABO-8il (colloidal silica). The entire mixture was then dispersed with a high shear mixer. This adhesive (4) exhibited thixotropic properties. T) JANOL SF
A similar adhesive (B) made from the -5505/PAPI 901 prepolymer was flowable. After curing for one week at ambient conditions, adhesive B
．． 6.78MPa' (compared to i7, 6.78MPa')
It had a tensile shear of 254 MPa (measured aluminum to aluminum by Ren 8TM-1002). , Example 3 This example demonstrates the use of the product of Example 1 in a soft foam formulation. Furthermore, ``This embodiment is based on THANOL
It is shown that fast setting foams with comparable properties can be made from this product compared to those made from the SF'-5505/PAP'I 901 prepolymer.

Blending ratio (parts by weight) A BTHANOL
SF-550550, 50 moisture
3.0 3.0 THAN
OAT TD -33” 0.3 0.3
THANOAT DM-7020,250,25NI
AX A -130,120,12 Polymer Prepolymer 4 134.25 -Prepolymer"
-L 116.9 Incyanate index 1.05
1.05 Manufacturing details Cream time (seconds) 12
12 rise time (seconds) 135
150 gel time (seconds)
150 195 special density CEL/cm3) 0゜07
0.05 tensile strength MPa)
0.133 0.121 Growth rate (chi)'
49 63 Tear strength, N
7 m) 2,31 2.14 Compression set (Method B) 50 inches 11.7 8.575 t
169.5 5.7 1: Triethylenediamine in propylene glycol (
33%): Texaco Chemical Company 2 dimorpholinodiethyl ether 70%/dimethylpiperazine 30%:
Texaco Chemical Co. 3: Bis(dimethylaminoethyl ether): Union Carbide Chemical Co.
Chemical corp, ) 4: Product of Example 1, incyanate content (meq/g):
z, s 3 5:50:50 THANOL SF'-550
5/PAP l9011 incyanate content (meq
/g) : 3.25 Example 4 Into a three-hole flask (11) equipped with a stirrer, a thermometer, a condenser, and a nitrogen supply line, a mixture of glycerol oxide with a molecular weight of 5500 / / ethylene oxide 7 (PO/D
o) Adduct (THANOL 5F-5505) 32
0g1 molecular weight 5000 butadiene liquid polymer ~ (LI
THENE N4-5000) 80 g and 2,5
-dimethyl-2,5-di(t-butylperoxy)hexa7 (LUPER8OL 101: trade name) 4.0
,1 was inserted. The reaction mixture was heated at 125-135° C. for 5 hours while maintaining a nitrogen purge. The product is then converted to 2,6-di-t-butyl-4-5ee-butyl7! /
-71z (l5ONOX 132) 1.39 te stabilized. The final product was a white, opaque, viscous liquid with the following characteristics: This polymer polyol was stable in glass for 3 months.

Acid value (mgKOH/g) 0.015 Hydroxyl value (mg KO'iVg) 3
2.6 Moisture (wt%)
0.01pH (lo:6 Improper Tool/Water) 68
Viscosity 25℃ (cps) 3
720 The physical mixture of the above reactants has an initial viscosity of 25°C.
and 1800 cps, and the phases separated within a few days.

Example 5 This example shows a scaled-up production according to Example 4. 301 reactor, THANO'L 5F-55
05 Polyol 3.63k19% LITHENE N4
-5000 0.9'lk! 9 and LUPER8OL
101 45.49 was input. The reactor was then evacuated and purged with previously purified hydrogen. Then, it was heated at 128-13.0°C for 3 hours. The reaction was monitored by measuring the viscosity every hour. The results are shown below.

Time (hours) Viscosity 25℃ (cpa) 0'
18601
21002
21003
2340 The product was then stabilized with di-t-butyl-p-cresol6,89. According to the GPO, the product appears on the chromatogram as 2 to 2 of the starting material.
It was 10% of the polymer with three times the molecular weight.

Example 6 This example demonstrates the use of the polybutadiene/polymer polyol of Example 5 in the production of RIM elastomers.

Additionally, this example shows that the hydrolytic stability and heat sag properties of elastomers made using these materials were improved. These elastomers were manufactured using an Accuratio machine.

I of of of Yes 　〇 Megaki To the prisoner Dimensions.

QcfI LO Eating Refill No. 1: Molecule Hssoo Glyse 1 Calorie with PO/EO: Texaco Chemical Co. 2: Obtained from Example 4 3: Molecular weight 11000 8Q: 20 EO/ PO diol: BASF Wyandotte
) 4: Dimethylaminoethanol: Texaco Chemical Co. 5: sur, -4 (Product name): Witco Chemical Co.
) 6: Thioorganotin compound: Upjohn Chemical Co., Ltd. 7: Liquid ■: Upjohn Chemical Co., Ltd.
Obemical Co, ) 8: Incyanato-rich pseudobrejo monomer: TH A
TE L-55-0' (trade name): Texaco Chemical Company Example 7 This example describes the preparation of polyfridiene polyturbo 1 (produced in Example 4) in a high-resilience (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 5F-550560 Polybutadiene polymer polyol
40 water
2.8Q2-5043 Silicone
2.0THANOAT T
D-330,25 NIAX A-130,25 THANOAT DM-7040,25 Dibutyltin dilaurate 0.01 80:2Q TDI/PAPI535.1 Isocyanate index 1.0
2 Manufacturing details Cream time (seconds) 6
Rise time (seconds) 12
0 gel time (seconds) 19
5 Characteristic density (r/CI/l)
o, o 38 tensile strength MPa)
0.092 Elongation rate (%)
119 tearing strength N/wrath)
2.28 Compression set 50%
21.195%
18.2 Compression set (%)
22.10LD loss, 50%6
9.991: DOW-Corning Corp. Manufacture 2: 33% trinoethylenediamine in propylene glycol: Texaco Chemical Co. 3: Bis-dimethylamine ethyl ether: Union.
Carbide Chemical Company 4nia 0% dimorphol/diethyl ether/30%+
7) N,N'-Dimeterpiverazine: Texaco Chemical Co. 5: High molecular weight ino-noanate with functionality of 2,7: Mobay Chemical C.
o+) Product 6: Compressive Load Deflection Example 8 This example demonstrates the polymerization of a hydroxyl-terminated polybutadiene liquid polymer in T)(ANOL 8F-5505 polyol).

Equipped with a stirrer, thermometer, condenser and nitrogen supply port f
Cl) in a three-loaf flask, THANOL 8F'-5
400 g of 505 polyol, hydroxy-terminated polybutadiene liquid polymer (: poly bd1
'L-45M (product name), Arco Chemical Company (ARO
OChemical Co. ), :l 100f and L
UP180L 101 (product name) 5.02 was introduced. At this point, the reaction had a viscosity of 1340 cps at 25°C.

The reaction mixture was heated for 4.75 hours while maintaining a nitrogen purge.
Heated at 128-135°C. The reaction mixture is then cooled and 15ONOX < 1320.5? It was stabilized.

The final product was a white, opaque, viscous liquid with the following characteristics:

Acid value (KOH/i?) 0.13 human oki'/g value (m9 KOH/f)
36.6 Moisture (wt%)
0.01 viscosity 25℃ (cps)
6300 peroxide (ppm)
1.95 Example 9 Into 11 three-bottle flasks equipped with a stirrer, thermometer, condenser and nitrogen inlet, propylene oxide/ethylene oxide/diglycidyl ether adduct of bisphenol A of glycerol with molecular weight 3500 400F, molecule -145
000 butadiene liquid polymer (LITHENE
N45000) 100 f and LUPEII, 5Q
L101 5.02 was introduced.

The reaction mixture was heated for 3 hours at 125° C. while maintaining a nitrogen purge.
Heated at ~135°C. The product was then stabilized with di-t-butyl-p-cresol 0175y. The final product was a white, opaque, viscous liquid with the following characteristics:

Human 0*7/l/value (my KOH/r)
42.3 Viscosity, 25℃ (cps)
1538 The physical mixture of the above reactants had a viscosity of 1275 CpS at 25°C.

Example 10 This real-world side demonstrates the use of the polymer polyol of Example 9 in the production of flexible foams. Furthermore, this example
Foams made with this polyol showed improved load carrying capacity compared to those made with glycerol propylene oxide/ethylene oxide (THANOL F-3016) with a molecular weight of 3000 and the base polyol of Example 9. show. Load capacity is Chatillon (0 bati)
llon) gauge (depression: 33%)
.

The blending ratio, manufacturing details, and foam characteristics are shown below.

1: Union Carbide Product 2: Triethylenediamine in propylene glycol:
Texaco Chemical Company Product 3: John Ohatill
on) Kumibi-Sans (5ons) Manual Model L.I.C.
Model LIO) Compression Tester ■472344 0 Inventor Richard Joseph Gilbert Dominguez 3107 Austin Canter Lane, Texas 78759, USA

Claims (1)

[Claims] 1. A method for producing a polyurethane-forming composition comprising an ethylenically unsaturated monomer, a crosslinked polymer obtained, and an active ingredient containing a free hydroxyl group or a free isocyanate group, wherein the active ingredient is A method for producing a polyurethane-forming composition, which comprises mixing with a liquid polymer obtained by polymerizing ethylenically unsaturated monomers in different media, and crosslinking the liquid polymer in the presence of the above-mentioned active ingredient. .