JPS5867710A - Liquid polymer composition - 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 This invention relates to modified polyurethane liquid polymer compositions.

The present invention relates to a specific liquid polymer composition containing a modified polyurethane oligo i- having terminal ethylenic unsaturation, a method for producing a polyurethane polymer using the liquid polymer composition, and a method for producing a polyurethane polymer by this method. polyurethane polymer products.

More particularly, in accordance with the present invention, it has been discovered that thermosetting liquid polymer compositions may be prepared that include a modified polyurethane oligo i- having terminal ethylenic unsaturation and a free radical-generating catalyst. Such compositions are characterized by the advantage of being one-component storage-stable systems that require only heat for activation. This composition is useful in making a wide variety of moldings, coatings and gel coats.

The polyurethane oligomers used according to the invention are prepared by reacting an organic polyisocyanate, a polyol, and an unsaturated monomer containing isocyanate-reactive groups. This reaction is carried out using methods well known in the art and from about 871 to about 2/1 and preferably about 17
It is carried out using relative ratios of the reactants to achieve an oligomeric product having an equivalent ratio of 1 to about 1.2/1 ONOO/OH. In the formation of oligo i-, approximately α
6/1 to about 25/1 and good 11. ．． < is approximately α871~
An isocyanate-reactive group-containing unsaturated monomer/polyol equivalent ratio in the range of about 1071 is used. Controlled molecular weight polyurethane oligomers with terminal reactive unsaturation are prepared by reaction of organic polyisocyanates, polyols, and unsaturated monomers containing isocyanate-reactive groups.

Preferably, this reaction is accelerated (by the use of a catalyst). Common urethane catalysts such as quaternary eynes and metal compounds such as tin-octoate or dibutyltin dilaurate can be used. Any amount of catalyst may be used; illustratively such amount varies from about 0.01 to about 1% by weight of the polyurethane oligomer depending on the particular catalyst used. It is also preferred to carry out this reaction in the presence of a reactive copolymerizable solvent. Suitable copolymerizable solvents include vinylidene compounds such as styrene, vinyltoluene, methacrylic esters, acrylic esters, cyhenylbenzene, and others well known to those skilled in the art. The amount of copolymerizable solvent used can vary over a wide range. Generally, however, the copolymerizable solvent will be used in an amount of from about 0 to about 100 parts by weight per 100 parts by weight of the polyurethane oligomer of the present invention.

Any suitable organic polyisocyanate or polyisocyanate mixture can be used in the preparation of the polyurethane oligomer; examples are toluene diisocyanate, e.g. 80:20 and 65:55 2.4- and 2.6-isomer mixtures. , ethylene diisocyanate, propylene diisocyanate, methylene bis(4-phenyl) isocyanate, xylene diisocyanate, 3.
According to a preferred embodiment of the invention h 2.
The weight ratio of alt to 2.6-isomer is about 60:
40 to about 90:10% and X>preferably about 45:3
An isomer mixture of 2.4- and 2.6-) luene diisocyanenites in a ratio of 5 to about 80:20 is used.

The polyol reactant used to form the polyurethane oligomer is selected from polyether polyols and mixtures of 2ff or more such compounds.

The polyol or polyol mixture is about 75 to about 500
It should have an average equivalent weight in the range of . Preferably the average equivalent weight
nt weight) is about 100 to about 200. Average functionality (av) of a polyol or polyol blend
Suitable polyether polyols include various polyoxyalkylene polyols and mixtures thereof. These are prepared using random or stepwise addition of alkylene oxides or mixtures of alkylene oxides to polyhydric hydroxyl (polyhydrtc) by well-known methods.
It can be prepared by condensation with an initiator or a mixture of polyhydric hydroxy initiators. Examples of alkylene oxides include ethylene oxide, propylene oxide, butylene oxide, alkylene oxide, aralkylene oxides such as styrene oxide and halogenated alkyl oxides such as trichlorobutylene oxide and others. The most preferred alkylene oxide is propylene oxide or mixtures thereof using random or stepwise oxyalkylation of ethylene oxide.

Koji's compounds and mixtures thereof are used as polyhydric hydroxy initiators conveniently used in the production of polyether polyol reaction components. (a) aliphatic triols such as glycerol, trimethylolpropane, trimethylolpropane, trimethylolhexane, etc.; (b) hydroxyl compounds such as tzmm, dextrose, sorbitol, kantaerythritol, methyl glucoside, etc.; <C) Polyabanes such as tetraethylenediazene, and ((11) flukanolamines such as diethanolazine, triethanolazine, etc.

A preferred group of polyhydric initiators for use in the preparation of the polyether polyol reaction component includes mixtures of sucrose, dextrose or methyl glucoside with aliphatic triols, preferably glycerol. The initiator condensation reaction is preferably carried out in the presence of a catalyst such as KOH, as is well known to those skilled in the art.

In carrying out the reaction, a sufficient proportion of alkylene oxide is used to provide a final polyol product having an average equivalent weight of from about 75 to about 500, preferably from about 100 to about 200. The catalyst is preferably later removed,
The polyurethane oligomer of the present invention is left with a polyether polyol prepared for use in KR.

Suitable isocyanate-reactive group-containing unsaturated monomers include acrylates and acrylamides, hydroxyethyl acrylate groups, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxyethyl acrylates, hydroxypropyl acrylates, butyl abanoethyl methacrylate, others and mixtures thereof. Acrylates are preferred, hydroxyethyl acrylate, hydroxyethyl acrylate and hydroxyethyl methacrylate are most preferred.

In the production of polyurethane oligomers, it is preferable to include a well-known chain extender in the polyurethane reaction mixture in the linear reaction mixture.These chain extenders include low molecular weight glycols such as ethylene glycol,
Examples include butanediol, hexanediol, propylene gelicol, tripropylene glycol, hisphenol A, and others. Other lenient chain extenders are about 20
The polyether polyol or polyether polyol mixture has an average equivalent weight ranging from 0 to about 4,000 and an average functionality of about 2. The amount of chain extender used can vary widely depending on the JHC of the polyol reactant used to make the polyurethane oligomer.

The modified polyurethane oligomer liquid polymer system is polymerized and cured in the presence of a thermally activated free radical-generating catalyst; the actual curing conditions can vary widely.

This, in turn, generally depends on the nature and amount of the particular catalyst used. Suitable free radical-generating catalysts include peroxide and azo type compounds known to those skilled in the art. All peroxide catalysts are organic peroxides and hydroperoxides, flJ, t if
knzoyl peroxide, diquine peroxide, methyl ethyl ketone peroxide, lauryl peroxide,
Cyclohexanone peroxide, tertiary butyl perbenzoate.

WJs class butyl hydroperoxide, 5-class butylbenzene hydroperoxide, cumene and do I peroxide,
Typical azo compounds are exemplified by tertiary butyl/zo-octoate and others such as azobisisobutyronitrile, 2-85-butyl gamma, 2-cyano-4-methylintane and 4-tert-butyl azo- 4-cyanoparelli γ
It is a noic acid. A preferred catalyst is a peroxide catalyst.

Particularly preferred peroxide catalysts are tertiary butyl peroctoate, tertiary butyl perbenzoate, and mixtures thereof.

Any suitable amount of catalyst can be used.

However, the catalyst is generally a polyurethane oligomer 10
It is used in an amount of about 0.1 to about 10 parts by weight.

The compositions of the invention may also optionally contain other standard ingredients such as internal WaS agents such as calcium, zinc, magnesium or sodium stearate. pigment,
Dyes, stabilizers, viscosity modifiers (such as Group I metal oxides and hydroxides such as magnesium oxide), thixotropic agents and various other additives well known to those skilled in the art may also be added.

The polyurethane liquid polymer compositions are generally stable for a reasonable period of time and are typically at least about 2 to
It can be stored for about 4 weeks. This composition is then cured by the application of heat to form a polyurethane polymer product that exhibits particularly desirable properties for coating applications. The cured product generally exhibits highly satisfactory hardness properties - yet it also has sufficient flexibility to resist crack formation.

The following examples are given to further illustrate the invention. All parts are by weight unless otherwise noted.

Polyurethane oligomer 〇 Production example 1 174t (2.0 equivalents) toluene diisocyanate isomer mixture (80:2002.4-/2.6-isomer mixture), 2B51 styrene, α071t hydroquinone and α142F 2.6-isomer mixture Di-tertiary butyl roux 4
-Methylphenol (BIT) Ks% with stirring
117.5f (0,8 wt) C) dlts x -thyl polyol (having a molecular weight of about 650 and an average functionality of about 4.25 and a sucrose/glycerol mixture and propylene oxide with a final hydroxyl number of about 375) 19.2
A mixture of a chain extender (trypite/glycol) of f (α2 equivalents) and an unsaturated monomer (hydroxyethyl acrylate) of 116F (1,0 equivalents) was added dropwise over a period of 2 hours. The reaction temperature increased from 21°C to 56°C.

The mixture was stirred without heating for 2 hours after the addition was complete. At this point 2B4f catalyst (50% stannous octoate in dioctyl phthalate, available from Liteco Rizucal Corporation under the designation rT-10J) was added. After stirring without heating for 15 minutes,
The reaction mixture was heated to 70°C and stirred at 70°C for 4 A hours. The product had a viscosity of 5200 ape at 25°C - Examples 2-10 Other polyurethane oligomers were prepared using the same conditions as Example 1 except for varying the reaction time at 70°C in the final step of the process. Manufactured.

0 Tables in which different reactants and reactant ratios were also used! outlines the oligomer compositions prepared according to Examples 2 to 10. Table I Oligomer Set 1 2.0 α8 α22
2.0 α6 α43
2.0 α2 Q, 6 c
L24 2.0 α2 α8
5 2.0 α6 - α20.
26 2, 0 Q, 8
α15 α057 2, On, 1 α1
- α88 2.0 α8
- α29 2.0 α2 -
0.8 -10 2.0
α2 [18 success 1.0 − 5200 4−−
1.0 4000 3μ0.5
15 640 4- 1.0
650 10- 1.0
3!500 5CL5 Q, 5
5! $50 7'A-1,03506 machine-1,05555i -1,05007 1,03'A ■ This diisocyanate is a mixture of toluene diisocyanate isomers (80:20 2.4-72.6-isomer mixture Il+ ).

■ Molecular weight of about 650 and average functionality t of about 4.25
-V and is a polyether polyol prepared by condensing a sucrose/glycerol mixture with propylene oxide to a final hydroxyl number of about 375.

■ An rt+ polyether polyol having a molecular weight of about 480 and an average functionality of about 4.54 and made by condensing a sucrose/glycerol mixture with propylene oxide to a final hydroxyl number of about 550.
■ Tripropylene glycol.

■ A polyether polyol having a molecular weight of about 425 and prepared by condensing propylene glycol with propylene oxide to a final hydroxyl number of about 265.

■ Hydroxyethyl acrylate.

■ Human mixipropyl acrylate.

■ Hydroxyethyl methacrylate.

Examples 11 to 19 of Preparation of Polyurethane Moldings Test/gunnels containing nine polyurethane oligomers were prepared according to Examples 1 to 9. A method of expansion has been established for the production of V-type panels.

This panel is α5% tertiary butyl peroctoate)
(commercially available from Rubersol Company under the name ``fppo'', consisting of 50% tertiary butyl peroctoate and 50% dioctyl phthalate) and (15% cumulative 5th butyl peroctoate and 50% dioctylphthalate). Manufactured for use as an agent.

(a) mixing a polyurethane oligomer with a free radical-generating catalyst and placing the resulting nine-thermal mixture in a vacuum desiccator at a pressure of about 1 to 10 torr for about 1 to 2 minutes or until initial bubbling has subsided; I was relieved by K.

(b) This evacuated mixture is prepared from a glass plate coated with a liquid mold release agent such as rMR515, J, commercially available from Greenchem Products, Inc. and held at a distance of an inch. Pour the mixture into a glass bottle.

(C) The mold was then held in the open at 120°C for 1 hour.

The physical properties of the nine panels produced in this manner are included in Table 1 below. This physical property was determined by standard test methods. Bending curvature and bending strength are A8'
I'M D 790, tensile strength and elongation as per ASTM
r) 3574 and eye knot strength is ASTM D2
According to 56. Percoll hardness is Coleman model 〇YZ,
Measured using a T 934-1 Impressor.

Comparative Example 1 For comparative purposes, polyester resin-containing Tes)/J flannel were produced according to the method of Examples 11-19.

In panel formation, polyurethane oligomers of Examples 1 to 9 were used.
A vinyl ester resin commercially available from the Dow Chemical Company under the designation J was used.

The physical properties of nine nonel manufactured by nature are shown in the table below.
included in. Physical properties - Measured by standard test methods.
D790, tensile strength and elongation are MUHITM D55
74% and the isorad value according to Mu8TM D256. Percoll hardness is Coleman model GYZJ 934
-1 It was measured using an inbretsucer.

Comparing the results, polyurethane oligo 1 of the present invention
- Panels made from conventional vinyl esters exhibit general properties at least comparable to, or better than, those shown by Sonel.9 In particular, these panels exhibit improved However,
This implies desirable flexibility and toughness properties. These properties are important in coating applications where resistance to crack formation is generally desired.

Claims (1)

Claims: 1) a polyurethane oligo i- and a thermally activated free radical-generating catalyst, and the polyurethane oligomer has an α of about 871 to about 2/1 Woo:
(IL) an organic polyisocyanate+111 polyol having an average equivalent weight of from about 75 to about 500 and an average blindness of at least about 5; and (0) an isocyanate-reactive group. Contains (1)
(M) nine unsaturated monomers selected from the group consisting of unsaturated acrylates, unsaturated acrylates, and mixtures thereof; 2) A polyurethane liquid polymer composition prepared by reacting using a monomer/polyol equivalent ratio. A composition according to claim 1, wherein the composition comprises: 5) The composition according to claim 2, wherein the copolymerizable solvent is styrene. 4) The polyurethane oligomer has a molecular weight of about 171 to about 1.2
A composition according to claim 1, having a Neo:OH equivalent ratio of /1. 5) The equivalent ratio of the isocyanate-reactive group-containing unsaturated monomer to the polyol is about α871 to about 10.
71. The composition of claim 4 in the range 71. 6) Said patent, wherein said unsaturated monomer is selected from hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxyethyl acryl azide, hydroxypropyl acrylide, tertiary butylaminoethyl methacrylate and mixtures thereof. 7) The composition of claim 6, wherein the unsaturated polymer is selected from hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and mixtures thereof. thing. 8) The composition of claim 1, wherein the thermally activated free radical-generating catalyst is a peroxide catalyst. 9. The composition of claim 8, wherein said peroxide is selected from S-butyl/tertiary butylnose octoate and mixtures thereof. 10) the polyol has an average equivalent weight of about 100 to about 200 and an average functionality of about 4 to about 6; and 2. The composition of claim 1, wherein the composition is prepared by reacting a hydroxyl initiator with an alkylene oxide selected from propylene oxide and mixtures of propylene oxide and ethylene oxide. 11) The polyurethane oligomer further includes a chain extender. A composition according to claim 1. 12) The composition of claim 111, wherein the chain extender is selected from tripropylene dalicol, polyols having an average equivalent weight ranging from about 200 to about 4000 and an average functionality of about 2, and mixtures thereof. thing. 13) The composition of claim 1, wherein the polyurethane oligomer is produced using toluene diisocyanate as the organic polyisocyanate. 14) the thermally activated free radical-generating catalyst is a peroxide catalyst and further the polyurethane oligomer has a NOO:OH equivalent ratio of about 171 to about 1.2/1 and is ) toluene diisocyanate, (t)l having an average equivalent weight of from about 100 to about 200 and an average functionality of from about 4 to about 6 and obtained from a mixture of sucrose, dextrose or methyl glycoside and aliphatic triols; polyether polyols prepared by reacting isolated polyhydric hydroxy initiators with alkylene oxides selected from propylene oxide and mixtures of propylene oxide and ethylene oxide;
and (C) an unsaturated monomer containing inocyanate-reactive groups selected from the group consisting of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, and mixtures thereof, having an isocyanate-reactive range H of from about 100 to about 1071. The composition according to claim 1, which is prepared by reacting the group-containing unsaturated monomer/polyol equivalent ratio. 15) The composition according to claim 14, wherein a copolymerizable solvent is included in the polyurethane liquid polymer composition. 16) The copolymerizable solvent is methylene. A composition according to claim 15. 17) The polyurethane oligomer contains a chain extender. 18) The chain extender is tripropylene glycol, about 200 to about 4. 18. The composition of claim 17, selected from polyols and mixtures thereof having an average equivalent weight in the Goo range and an average functionality of about 2. 19) mixing a polyurethane oligomer and a thermally activated free radical-generating catalyst and then heating the mixture to a temperature sufficient to activate the catalyst and cure the mixture, and The polyurethane oligomer has a W of about α671 to about 271
oo : 01 (has an equivalence ratio and it is (IL
) an organic polyisocyanate, (DJ) a polyol having an average equivalent weight of from about 75 to about 500 and an average functionality of at least about 3, and (o) an isocyanate-reactive group; (1) an unsaturated acrylate (II); unsaturated monomers and (110 mixtures thereof)
Producing a polyurethane polymer-forming eyelid, characterized in that it was produced by reacting using an unsaturated monomer containing isocyanate-reactive groups/polyol ratio in the range of about 2571%. 20) mixing a polyurethane oligomer and an A-oxide catalyst and then heating the mixture to a temperature sufficient to activate the catalyst and cure the mixture; MOO with ff - of about 171 to about 1.2/1: 011
(a) toluene diisocyanate, (b) sucrose, dextrose, having an average equivalent weight of about 100 to about 200 and an average functionality of about 4 to about 6; It was prepared by reacting a polyhydric initiator derived from a mixture of methane dilucoside and an aliphatic triol with an alkylene oxide selected from propylene oxide and a mixture of propylene oxide and ethylene oxide. a polyether polyol, and (C) an isocyanate-reactive group-containing unsaturated monomer selected from the group consisting of human prize xyethyl atarisheet, dipropyl acrylate, hydroxyethyl methacrylate, and mixtures thereof; 21) The method of claim 19, wherein the incyane F reactive group-containing unsaturated monomer/polyol weight ratio is in the range of about 1071. Claim 20, wherein the polyurethane oligomer is prepared by carrying out the reaction in the presence of a styrene copolymerizable solvent and promoting the reaction by the use of a urethane catalyst. 22) A chain extender in which the polyurethane oligomer further comprises tripropylene glycol, a polyol having an average weight in the range of about 200 to about 4,000 and an average functionality of about 2, and mixtures thereof. 22. The method of claim 21, comprising: 25) A polyurethane polymer product produced by the method of claim 21). 24) A polyurethane polymer product produced by the method of claim 20 above. 25) Claim #l! ! 22. A polyurethane polymer product produced by the method of item 21. 26) A polyurethane polymer product produced by the method of claim 1ffi@22.