DE2353855A1 - PROCESS FOR MANUFACTURING UNSATATULATED POLYURETHANE RESINS - Google Patents

Description

Dr. F. Zumstelm Sr. - Dr, E. Assmann.
Dr. R. Koenigsberger - Dlpl.-Phys. R. Hoizbauer - Dr. F. Zumsteln Jun.

PATENT LAWYERS

TELEPHONE: COLLECTIVE NO. 22S341

. TELEX 529979 TELEGRAMS: ZUMPAT-

CHECK ACCOUNT: MUNICH 91139-809, BLZ 7OO10O80 BANK ACCOUNT: BANKHAUS H. AUFHÄUSER

ACCOUNT NO. 397997, bank code 70030600

8 MUNICH 2.

BRAUHAUSSTRASSE *

97 / N "..

Case F-1139-K53 (DIC) / hF

DAINIPPONINKANDCHEMICALS, INC., Tokyo / Japan

Process for the production of
• unsaturated polyurethane resins

The invention relates to a method for producing a new and valuable unsaturated polyurethane resin. In particular the invention relates to a method of production of an unsaturated polyurethane which can provide crosslinked cured products that are not only in terms of resistance to chemical attack and are excellent in mechanical properties, but also have a high softening temperature or heat resistance (heat distortion temperature), and further a method for producing an economically valuable unsaturated polyurethane resin Providing a resinous solution with a considerable improved storage stability. '

It was previously known to be either acrylic acid or methacrylic acid to react with an epoxy compound which has one or more epoxy groups in its molecular structure,

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to obtain a compound that contains one or more acrylic or methacrylic groups in its molecular structure.

However, most commercially available epoxy resins are those which have epoxy groups at both ends of the molecular structure or the molecule, with the result that the compounds obtained by the reaction of an epoxy group and either acrylic or methacrylic acid, as described above, are only oligomers, which have at most 2 acrylic or methacrylic groups in the molecule. Although attempts were still made to increase the unsaturated bonds in the molecular structure through polymerization by further reacting these oligomers with a saturated or an unsaturated dibasic acid, undesirable side reactions occurred, such as etherification with ring opening and esterification with formation. branching, which caused gelation to occur during the reaction, or only products whose solubility in the polymerizable vinyl monomers was low could be obtained. Accordingly, even in the case of the cured products obtained therefrom, it was only possible to obtain those which had limited performance in terms of such properties as chemical resistance, heat resistance and mechanical properties.

The aim of the invention is to eliminate these disadvantages of the prior art.

It has been found that the unsaturated polyurethane resin obtained by reacting an ester compound with a certain epoxy compound and an unsaturated monobasic acid (unsaturated epoxy ester) with a diisocyanate compound in a polymerizable vinyl monomer in the "presence or." Absence of an oligopolyester glycol containing a saturated or unsaturated dibasic acid group (im hereinafter referred to as "oligoglycol") is easily obtained with the above polymerizable vinyl monomer at room temperature or under heating or subjecting High-energy rays polymerized to form a cross-linked

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hardened product with high chemical resistance, heat resistance and also an extremely high softening temperature and is therefore suitable for such purposes as molding, laminating and coating or lining. It has also been found that when a monoalkyl ester an unsaturated dibasic acid of a polymerizable monomeric solution of this unsaturated polyurethane resin for Was added at the time when the urethane formation reaction was completed, a resinous solution could be obtained, which had significantly improved storage stability.

Accordingly, the present invention provides a method of manufacture a solution of an unsaturated polyurethane resin in one polymerizable vinyl monomers, characterized in that roan

A) an unsaturated epoxy ester, an ester of an epoxy compound with 2 epoxy groups in their molecular structure, however, which does not contain a hydroxyl group, and an unsaturated one monobasic acid

B) a diisocyanate in a polymerizable vinyl monomer in the presence or absence of

C) an oligopolyester glycol, which is a saturated or contains unsaturated dibasic acid,

converts, as well as a method for producing, a solution an unsaturated polyurethane resin in a polymerizable one Vinyl monomers that have a significantly improved storage stability has, which is characterized in that one

D) a monoalkyl ester of an unsaturated dibasic acid of the heart-shaped solution after the end of the urethane reaction admits »,.

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In general, the unsaturated polyester resins provide cured products which have relatively very good properties, and furthermore, these resins have good processability. As a result, the unsaturated polyester resins are wide spread. On the other hand, it is known that the unsaturated polyurethane resins produced by the unsaturated polyesters with a urethane bond can be obtained in its molecular structure, both an even better chemical resistance and solvent resistance as well as have improved mechanical properties. When making an unsaturated Polyurethane resin of this type it is necessary to react with a diisocyanate after thorough dilution of the unsaturated polyester with a polymerizable vinyl monomer, which is inert to the isocyanates, such as a styrene monomer, to be carried out. However, in the case of one Reaction at high concentrations as a result of side reactions, the formation of bonds such as allophanate bonds, one, which is due to the high reactivity of the isocyanates, so that the risk of gelation as a result the sudden increase in the viscosity of the system. If the double bonds continue to polymerize while this urethane reaction occurs, gelation will occur be done immediately. Particular attention must therefore be paid to preventing the polymerization reaction.

In order to prevent gelation during the production of the unsaturated polyester resins or during storage, it is common practice to add a polymerization inhibitor. As such a polymerization inhibitor, the phenolic compounds are generally used. Among these, tert-butyl catechol and hydroquinone are particularly valuable because of their good solubility and great effectiveness. However, these compounds can not be added during the preparation of the unsaturated polyurethane resins because, since these compounds contain active hydrogen atoms, they react with the included System isocyanate component and thus do not develop their inherent polymerization inhibitory activity, with the result _s that the

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Storage stability of the resin decreases considerably. But also, when the above polymerization inhibitors the unsaturated polyurethane resin after the urethane reaction or during were added to its storage was the storage stability obtained from a practical point of view only partially satisfactory.

As a result of extensive research to improve the storage stability of such polyurethane resins, it has been found that this storage stability depended on the acid number of the resinous solution, and it was also found that by using a monoalkyl ester of an unsaturated dibasic acid not only the storage stability is increased considerably, but also the properties of the hardened one Product have not been deteriorated »

The above unsaturated epoxy ester (A) used in the process of the present invention is either a diacrylate or a dimethacrylate of an epoxy compound. which is the reaction product is obtained by the esterification reaction between an unsaturated monobasic acid, such as acrylic or methacrylic acid, and an epoxy compound, the Has 2 epoxy groups in its molecular structure, but does not contain a hydroxyl group. The above epoxy compound is either diglycidyl ether or dimethyl glycidyl ether obtained are made by the reaction of either an epihalohydrin or ß-methylepihalohydrin with: either a divalent one Alcohol, a dihydric phenol or a dibasic acid in the presence of an alkaline compound, or the corresponding esters of these digylicidyl ethers or dimethyl glycidyl ethers, and denotes those "low molecular weight epoxy compounds or alicyclic diepoxy compounds, which contain essentially no hydroxyl groups.

The esterification reaction between these epoxy compounds and the unsaturated monobasic acids, such as acrylic or methacrylic acid, · Is best at a temperature in the range of 60 to 150 ° C, and preferably 80 to 120 ° C, at a molar ratio carried out from epoxy compound to acid of 1: 1 to 1: 2.

-.409-820 / 1053 '

To achieve a shortening of the reaction time and also the occurrence of undesirable side reactions, such as ring opening and etherification of the epoxy groups, it is desirable to when carrying out the reaction 0.01 to 1% by weight, based on the reaction mixture, a tertiary amine or a salt thereof, an inorganic metal salt, such as sodium chloride, potassium chloride and lithium chloride, or a salt of an organic acid such as sodium acetate, Potassium acetate and lithium acetate.

Furthermore, in order to avoid polymerization, it is desirable during this esterification reaction a polymerization inhibitor such as hydroquinone and tert-butyl catechol in. in an amount of 50 to 5000 ppm, and preferably 100 to 1000 ppm.

According to a preferred embodiment of the invention then, the thus obtained unsaturated epoxy ester (A), a diacrylate or a dimethacrylate of an epoxy compound in min-, at least one polymerizable vinyl monomer or a mixture dissolved by two or more of them, after which the polyurethane reaction by adding a diisocyanate compound (B) is carried out in the presence or absence of an oligoglycol (C), which is obtained by reacting 2 to 4 moles of a glycol with 1 to 3 moles of a saturated or unsaturated dibasic acid was obtained.

As the polymerizable vinyl monomer to be used in order to dissolve the unsaturated epoxy ester (A), the following typical compounds may be mentioned: styrene or its derivatives, acrylic esters, methacrylic esters, acrylonitrile and methacrylonitrile. The amount in which these polymerizable vinyl monomers are used should be such that the viscosity of the unsaturated polyurethane solution resulting from the urethane reaction does not adversely affect its processability and the properties of the cured product. In general, a monomer concentration of about 10 to 60 % is advantageous.

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As for the production of the above oligoglycol (C) too Glycols used are those known, "commonly used glycols, such as ethylene glycol-1, propylene glycol, diethylene glycol, Triethylene glycol, 1,6-hexanediol and butanediol, called. On the other hand, the unsaturated dibasic acids mean such known, commonly used "unsaturated dibasic acids" Acids such as fumaric acid, maleic acid, maleic anhydride, citraconic acid and itaconic acid. Saturated dibasic acids are understood to be acids such as succinic acid, Succinic anhydride, adipic acid, sebacic acid, phthalic acid, phthalic anhydride, isophthalic acid and terephthalic acid.

From the above term "diisocyanate compound (B)" typically include such compounds as tolylene diisocyanate, 3,3'-bitolylene-4,4'-diisocyanate, diphenylmethane-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate, m-phenylene diisocyanate, naphthylene-1,5-diisocyanate, hexamethylene diisocyanate, Xylylene diisocyanate and 1,4-tetramethylene diisocyanate, or the dimers of these diisocyanates. Furthermore, the addition compounds of these diisocyanates with compounds that contain active hydrogen, suitable as a diisocyanate compound according to the invention. Examples of these active hydrogen containing compounds include ethylene glycol, propylene glycol, Tetramethylene glycol, neopentyl glycol, butanediol, 1,6-hexanediol, Polyethylene glycol, polypropylene glycol, bisphenol-ethyl enoxide adduct, bisphenol propylene oxide adduct, etc.

These diisocyanate compounds (B) are used in an amount of 0.2 to 1.0 times calculated as isoeyanate groups based on the hydroxyl groups contained in the reaction system, that is, in a ratio of 0.2 to 1.0 mol of isocyanate groups per mole of hydroxyl groups "

During the urethane reaction, preferably at one temperature is carried out from 40 to 100 ° C, it may be necessary to increase the temperature because of the rapid reaction process depending on the reactivity of the diisocyanate used

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Compound and the reactivity of the unsaturated epoxy ester (A) or the hydroxyl group of the oligoglycol used (C) to avoid. To achieve this, it is preferred to add the diisocyanate compound in portions or with the above to dilute polymerizable vinyl monomers.

On the other hand, the addition products of the diisocyanates and the various above, active hydrogen-containing compounds are formed. For example, the above derived from epoxy compounds Diacrylate or dimethacrylate (A) are mixed with one of the various glycols above, after which the diisocyanate is admitted. Alternatively, the desired unsaturated polyurethane resin can be produced, for example, by a method which consists in that in the presence of an oligopolyester glycol (C) obtained by reacting any of the above Glycols with an organic acid, such as succinic acid, adipic acid, azelaic acid, sebacic acid, maleic anhydride, Fumaric acid or phthalic acid, a diisocyanate compound (B) to the diacrylate or dimethacrylate (A) in a 0.2 to 1.0 fold Amount, calculated as isocyanate groups, based on the total hydroxyl groups contained in (C) are added.

The thus obtained solution of an unsaturated polyurethane resin in the polymerizable vinyl monomer of the present invention is valuable in such fields as molding, lamination and painting, and can be obtained by adding a redox catalyst such as cobalt naphthenate methyl ethyl ketone peroxide, dimethyl aniline benzoyl peroxide, cobalt naphthenate acetylacetone. Peroxide and vanadium naphthenate methyl ethyl ketone peroxide, easily hardened at room temperature. It may also with the addition of a peroxide, such as benzoyl peroxide, cumene hydroperoxide or di-t-butyl peroxide, can be cured by heating at 50 to 150 ⁰ C. The cured products obtained in this way have excellent mechanical and electrical properties and also have superior chemical resistance, solvent resistance and an extremely high deformation temperature (heat distortion temperature),

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There are cases where the acid number of the 'solution is an unsaturated Polyurethane resin in polymerizable yinyl monomers, which was obtained according to the invention, decreases during the urethane reaction, so that the desired storage stability despite Addition of a polymerization inhibitor cannot be achieved. In such a case, the storage stability of the resinous Solution can be improved by adding the above monoalkyl ester of unsaturated dibasic acid (D). The decrease in storage stability that can be attributed to this drop in acid number is probably due to the following: If the acid number in a system is high, the polymerization inhibitor present in the system is full or present unabated, with the result that its effect as a 'radical scavenger is fully developed. On the other hand, if the acid number is low, it is presumed that the polymerization inhibitor which is easily oxidized by the oxygen in the air leads to a decrease in the stability of the system within a short period of time. If that seems to be the reason, then the Adding an acidic substance, a carboxylic acid or yours Esters together with the polymerization inhibitor the storage stability of the solution of the unsaturated polyurethane resin, their Acid number is low, improve. However, from the investigations, it was found that sometimes it tends to decrease the storage stability of the unsaturated polyurethane resin solution and a decrease in the properties of the obtained cured one Products occurred, depending on the type of acidic substance added in this case, and that .only the monoalkyl esters the unsaturated dibasic acids (D) could serve the purpose.

As an unsaturated dibasic acid, one of the components of The above monoalkyl esters are dibasic acids such as maleic acid, fumaric acid, itaconic acid, gitraconic acid, and such anhydrides as maleic anhydride, itaconic anhydride and citraconic anhydride are called. As monohydric alcohol, the other component of the monoalkyl ester, are also the lower aliphatic monohydric alcohols such as methanol, Ethanol, isopropanol and butanol.

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The monoalkyl esters can be prepared by a dehydroesterification reaction between an equimolar amount of the above unsaturated dibasic acids and the monohydric alcohols. The desired monoalkyl ester is obtained very easily and quantitatively advantageously by a process in which an equimolar amount of an acid anhydride is reacted with a monohydric alcohol at a low temperature. Thus, the most advantageously useful monoalkyl ester (D) from the economical point of view is monomethyl maleate obtained from maleic anhydride and methanol.

As the storage stability of the unsaturated polyurethane resin solution is bad, when the acid value is less than 5, it is necessary to add the above monoalkyl ester (D) to increase their acid number to at least 5, and preferably 10-20. The addition of the monoalkyl ester to the unsaturated polyurethane resin solution is preferably carried out at the time of termination of the urethane reaction.

The following examples further illustrate the invention.

Reference attempt 1 Production of a dimethacrylate of an epoxy compound

To 210 g of a resin of the bisphenol A bis (glycidyl) ether type, made from 1 equivalent of bisphenol-A, 5 to 10 equivalents Epichlorohydrin and 1 equivalent of sodium hydroxide (under the trade name EPICHLON 850 from DAINIPPON INK & CHEMICALS, INC. produced, epoxy equivalent = 2OO), 86 g of methacrylic acid, 200 ppm hydroquinone and, as esterification catalyst, 0.1% by weight, based on the total charge, triethylamine admitted. The mixture was then allowed to react for 10 hours at 80 ° C. while stirring and passing in an inert gas brought to obtain a dimethacrylate with an acid number of 3. The dimethacrylate thus obtained was then in 200 g Styrene dissolved to give a light yellow colored resinous solution having a viscosity of 50 centipoise.

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Reference attempt 2 .

Production of a dimethacrylate of an epoxy compound

To 230 g of a resin of bisphenol A bis (2-methylglycidyl) ether type, made from 1 equivalent of bisphenol-A, 5 to 10 equivalents of ß-methylepichlorohydrin and 1 equivalent of sodium hydroxide (manufactured under the trade name EPICLON MH-8 by the above company, epoxy equivalent = 220) j was 86 g Methacrylic acid, 300 ppm hydroquinone and 0.2% by weight, based on the entire batch, triethylamine were added. The reaction was then carried out as in Reference Example 1 for 15 hours to obtain a dimethacrylate having an acid number of 4.5 to obtain. The dimethacrylate thus obtained was then in 210 g Styrene to form a light yellow heart-shaped solution dissolved at a viscosity of 250 centipoise.

Reference attempt 3 Production of a dimethacrylate of an epoxy compound

A resin of the neopentyl glycol bis (2-methylglycidyl) ether type, made from 1 equivalent of neopentyl glycol, 5 to 10 equivalents of ß-methylepichlorohydrin and 1 equivalent of sodium hydroxide (manufactured by the above company under the trade name EPICLON 720, epoxy equivalent = 130) was used in an amount of 140 g was used and the reaction was carried out at 100 ° C. for about 15 hours. The experiment was otherwise as in Reference experiment 2 carried out umi a dimethacrylate with a Acid number of 4 to be obtained. The dimethacrylate thus obtained was then dissolved in 160 g of methyl methacrylate to make a dimethacrylate solution with a viscosity of 10 centipoise.

Reference attempt 4 -

Preparation of a diacrylate of an epoxy compound

To 350 g of a resin of the hexahydrophthalic acid bis (2-methylglycidyl ether) ester type, made from 1 equivalent of hexahydrophthalic acid, 5 to 10 equivalents of ß-methylepichlorohydrin and 1 equivalent of sodium hydroxide (trade name: EPICLON 400,

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Product of the above company, epoxy equivalent = 330) 72 g of acrylic acid, 400 ppm of hydroquinone and 0.2% by weight, based on the entire batch, of triethylamine were added. The reaction was then carried out as in reference experiment 1 for 20 hours with formation of a diacrylate with an acid number of 5. The diacrylate thus obtained was then dissolved in 280 g of styrene to form 700 g of a styrene solution having an acid number of 6 and a viscosity of 20 centipoise.

Reference attempt 5 Production of a dimethacrylate of an epoxy compound

To 460 g of S ^ -epoxy-e-methylcyclohexyl-S ^ -epoxy-e-methylcyclohexane carboxylate (Trade name UNOX ERL 4201, product of Union Carbide Corporation) with an epoxy equivalent of 153 250 g methacrylic acid, 25O ppm hydroquinone and Ο, 14 g potassium chloride added, after which the mixture was reacted for 10 hours at 85 ° C to give a dimethacrylate with an acid number of 5 to obtain. The dimethacrylate thus obtained was then dissolved in 470 g of styrene to form a light yellow colored resinous shape Solution with a viscosity of 180 centipoise dissolved.

Attempt 6 Production of an oligopolyester glycol

1 mole of phthalic anhydride and 2 moles of ethyl closely lykol were 5 hours reacted at 200 C with the introduction of an inert gas, an oligopolyester glycol having a hydroxyl equivalent of , 150 and an acid number of 2 was obtained.

Reference attempt 7 Production of an oleopolyester glycol

1 mole of fumaric acid and 2 moles of neopentyl glycol were introduced an inert gas reacted for 8 hours at 2OO ° C, wherein an oligopolyester glycol with an acid number of 1.2 and one hydroxyl equivalent of 160 was obtained.

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Reference attempt 8 ■

Preparation of a diisocyanate adduct

After heating 2 mol of tolylene diisocyanate to 40 ° C was 1 mol of diethylene glycol was added dropwise over 3 hours. After the addition was complete, the reaction was carried out at 60 ° C. for 2 hours, using a diethylene glycol-tolylene diisocyanate adduct with an isocyanate equivalent of "220 became.

Reference attempt 9 Preparation of a diisocyanate adduct

2 mol of xylylene diisocyanate were heated to 40 ° C, after which 1 mol Dipropylene glycol within 3 hours while cooling the mixture was added dropwise. After the addition was complete the mixture was kept at 60 ° C. for a further 3 hours, a dipropylene glycol-xylylene diisocyanate adduct with an isocyanate equivalent of 251 was obtained. . .

Reference attempt 10 Production of an oligopolyester glycol

1 mol of fumaric acid, 2 mol of neopentyl glycol and 200 ppm of hydroquinone were ^{reacted for 8 hours at 200 °} C. while introducing an inert gas, an oligopolyester glycol with an acid number of 1.2 and / a hydroxyl equivalent of 160 being obtained.

Examples T to 7 \

By adding 60 percent by weight styrene solutions drop by drop of the various types of diisocyanate compounds given in Table I. for 1 hour with stirring to form solutions of a diacrylate or dimethacrylate of an epoxy compound in the Virtyl polymerizable monomer obtained in Reference Runs 1 to 5 using a molar ratio of. Hydroxyl group to isocyanate group as indicated in the table, urethane reactions were carried out. . . ·.

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The other conditions of the reactions and the properties of the solutions thus obtained of the unsaturated polyurethane resins in the polymerizable vinyl monomers and the properties of the cured products are summarized in table Ϊ.

The table also shows the properties of a comparative sample (use of bisphenol-A-modified polyester) specified.

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ORIGINAL iMSPECTED

Table I. example

comparison

Bisphenol A modified Iz polyester

Diacrylate or dimethacrylate component used

Diethacrylate of reference experiment 1

Dimethacrylate of reference experiment 2

Dimethaerylate of the reference εν he seeks s 3

Reference trial diacrylate

Reference trial dimethacrylate 1

Dirnethacrylate des
Reference attempt
3

Dimetha- '
crylate des
Reference attempt
5

Diisocyanate component used

Tolylene

di-, isocyanate:

Tolylene

di-

isocyanate

Tolylenedi- ■
isocyanate

Xylylene * "isocyanate

Xylylene

di-

isocyanate

Hexamethylene

lendi-

isocyanate

H exameth ylendi-

isocyanate

Molar ratio Hydroxyl group / isocyanate

1 / 0.6

1 / 0.7

1 / 0.8

1 / 0.6

1 / 0.8

1 / 0.6

1 / 0.5

Reaction temp., ( ⁰ Ci.

60

60-

5Q.

60

70

Response time (hours) '

Viscosity of the product solution CcP)

450

600

1,500

450

1,200

150

50:

210

in I.

Gel time d. Product v (minutes)

2 -

1 - 2

2 - 3

co cn co oo cn cn

Softening temp. (° C) ⁺⁺

Flexural strength
(kg / mm ² ) ⁺⁺⁾

142

14.2

121

10.5

128

15.2

115

; 16.1

138

12 _r 7

120

9.5

Table I (port setting)

CD OO K5 O

cn approx

• '++)
Chemical resistance
[Swelling ratio (%) after 60 ⁰ C χ -0.02 -0.03 5 hours] 0.21 0.09 -0.02 -0.01 -0.07 20% HCl 0.06 0.06 -0.01 0.10 0.02 0.08 0.05 0.97 20 % aq. NaOH 0.31 0.25 0.05 0.41 0.15 0.42 0.20 0.82 25% WaB-H ₂ SO ₁ 0.81 0.91 0.32 0.98 0.21 1.01 0.40 1.30 Methylethyl
ketone 0.06 0.05 1.20 0.12 0.04 0.09 0.21 0.72 Styrene 0.05 0.04 0.08 0.05 0.01 0.08 0.02 0.59 25 % aq.
acetic acid 0.02. 0.03 0.10 0.04 0.03 0.03 0.02 0.33 10% aq.
Sodium hypo-
chlorite solution -0.02 -0.03 -0.05 -0.03 0.001 -0.05 -0.15 0.28 Xylene 0.01

cn

The determination of the gel time was carried out according to the SPI method using of 0.4 part by weight of 6% cobalt naphthenate and 1.0 part by weight of methyl ethyl ketone peroxide per 100 parts by weight of the resin.

The sample of the cured product that was used in tests to determine the softening temperature, flexural strength and chemical resistance was one obtained by adding 0.4 parts by weight of 6% cobalt naphthenate and 1.0 part by weight of methyl ethyl ketone peroxide ζυ 100 parts by weight of the Resin and subsequent curing of the product by standing for 16 hours at room temperature (25 ° C) and then for 3 more hours at 110 ⁰ C was produced.

Examples 8-11

The Oligopo.ly ester glycols obtained according to the reference experiments and 7, as shown in Table II, the various diacrylates and dimethacrylates of the epoxy compounds were obtained in the reference experiments 1 to; 4, added, after which the respective polymerizable vinyl monomers used during manufacture the diacrylates or dimethacrylates were used, were further added to the various mixtures, namely in such an amount that the solids content of the mixtures in With respect to these oligopolyester glycols accounts for 60%. A 60 weight percent solution was then added dropwise to the mixtures of tolylene diisocyanate in the polymerizable vinyl monomer was added dropwise within 1 hour, after which the reaction (Go Urethane reaction) during the time indicated in Table II was carried out to obtain polymerizable vinyl monomer solutions of unsaturated polyurethane resins.

The reaction conditions and the properties of the resinous solutions obtained, as well as the properties of the hardened one Products are given in Table II. For comparison purposes, the properties of a comparative sample are also included in the same Given in the table.

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- Table e II 8th Dimethacrylic
• lat des
Reference
attempt 2 590 , 10 11 comparison 12th (l) Di-
acrylate or di-
methacrylate
component Dimethacrylate
of the reference
attempt 1 obtain
according to Be
Zugsvers 7 2.0 Whore thacryl at
of the reference
attempt 3 Dimethacrylic
lat des
Reference
Trial 4 D.imethacry-
lat. one
Epoxy
link (2) Oligo used
poly ester glycol Example · . received
. measure reference
attempt 6 7/3 *
received according to
Reference attempt
6th received ge
according to reference
attempt 7 ■ Τ
Ο
co @ / © molar ratio 7/5 0.8 6/4 .5 / 5 • ocr
K)
O
O
cn
Ca) Hydroxyl groups /
Isocyanate group
MoI ratio 0.6 50 0.9 Reaction tempera
tur ( ⁰ C) 50 3 60 60 Reaction time (hours) 4.5 " 5 3.5 Viscosity of the pro
product solution (CP) 340 980 580 Gel time of the product
(Min.) +). 1.0
I. 3; 5

«. Table II (Continuation) 10 11 comparison Softening temperature
( ⁰ C) ' ⁺⁺⁾ example 120 , 102 Dimethacrylate
an epoxy
link Flexural strength (kg / mm ² ) ⁺⁺⁾ • 8th 9 13.5 16.1 115 Chemical resistance of the
hardened product ⁺⁺ ) 125- ■: 131 9.8 £ * ■
O Degree of swelling (%)
after 23 ° C χ 30 days] IA, 3 15.0 CO
CS
κ>
ΓΊ 20% HCl 0.08 -0.31 O 20% aq. NaOH. 0.07 0 _f 12- . 0.35 ·. 01
approx ? 5% aq. H ₂ SO ^ -0.05 0.02 0.12 0 _T 49 0 _r 41 Methyl ethyl ketone. 0.08 0.10. 0.18 0 _T 81 0 _T 31. Styrene OjAl 0.03 0.05 0.03 o, 95: 25% aq. acetic acid 0 _? 42 0.12 0.03 0 _r 01 . ^o r31 10% aq. Sodium hypochlorite
solution 0.08 0.09 : OtOI 0.02 • 0.42 Xylene. 0.0 ^ · 0.01 0 _r 10 -0 _f 08 0.05 "0.01 0.03 0 _y 02 . -0.05 0.08

+) as in table I ++) as in table I

oil cn

LO vJ OO ü U - 20 -

Example 12

180 g of a 60 percent strength by weight styrene solution of the diethylene glycol addition product of tolylene diisocyanate obtained in Reference Experiment 8 was added dropwise to 500 g of a 60 weight percent Styrene monomer solution of a dimethacrylate of an epoxy compound, obtained according to reference experiment 1, added within 1 hour. The reaction was carried out to turn a light yellow colored resinous solution having a viscosity of 150 centipoise at 25 ° C.

When 1 part by weight of methyl ethyl ketone peroxide and 0.4 part by weight of 6% cobalt naphthenate were added to the resinous solution thus obtained and the mixture was hardened, an extremely tough hardened product with a softening temperature and a flexural strength of 110 ^° C. or 18.5 kg / rnifi received.

Example 13

260 g of a 60 percent strength by weight styrene solution of a dimethacrylate an epoxy compound, obtained according to reference experiment 2, and 210 g of a 60 percent strength by weight styrene solution of the dipropylene glycol-xylylene diisocyanate adduct, obtained according to reference test 9, were, as indicated in example 12, implemented to a light yellow colored resinous solution with a viscosity of 210 centipoise at 25 ° C.

As 1 part by weight of methyl ethyl ketone peroxide and 0.4 part by weight 6% cobalt naphthenate was added to the resinous solution thus obtained, and the mixture was hardened extremely tough hardened product with a softening temperature and a flexural strength of 130 ° C and 17.8 kg / mm, respectively.

Example 14 '

The dimethacrylate of an epoxy compound obtained according to reference experiment 1, was mixed with the oligopolyester glycol obtained in reference experiment 10 in such an amount that the ratio

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the former to the latter was 7/3, according to which these are polyester glycols by adding monomeric styrene in such a cruet that the solids content of the solution is 60% became." . * ' -", . ·

The urethane reaction was then carried out by adding a 60 percent strength by weight styrene solution of tolylene diisocyanate to the solution of polyester glycols in styrene monomer prepared in this way at 50.degree. C. in such an amount that the isocyanate group content is 60 % of the total hydroxyl groups. An unsaturated polyurethane resin solution with an acid number of 0.2 and a viscosity of 3'40 centipoise was thus obtained.,

Example 15 . .

Monomethyl maleate was added to the various unsaturated polyurethane resin solutions, which had been obtained according to Examples 1, 2 and 14, added in such amounts that the acid numbers of the resinous solutions gradually range from 0 to 20, after which 500 ppm of hydroquinone are further added and stirred thoroughly. These solutions were each dn round. Container with a capacity of 1 kg introduced, closed and stored in a thermostated chamber at 25 ° C. The formation of the gelled product on Bottom of the container was checked once a day with a glass rod, and the number of days that had passed was determined, until gelled material adheres to the glass rod, wherein the results given in Table III were obtained.

For comparison, the same test on a sample consisting of the resin obtained according to reference test 1, which in the same Manner as described above except that methacrylic acid was added to the resin, ■ carried out -. _ -_. . / ·.> , ■

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Table III Number of days elapsed for gelled to form

material

Acid number 0 5 10 13th 20th sample less than 1 day 7 days 40 days 63 days 70 days Resinous
Solution of the
Example 1 fl 10 45 64- 73 Resinous
Solution of the
Example 2 ti '.
Il 5
3 33
18th 55
25th 65
31 Resinous
Solution of the
Example 14
comparison

Example 16

Monomethyl itaconate was added to the various unsaturated polyurethane resin solutions obtained according to Example 1, 2 and 14 added in such amounts that the acid numbers of the resinous Solutions gradually ranged from 0 to 20 at which point an additional 50 ppm hydroquinone was added and stirred thoroughly. The storage test was carried out on these mixtures as indicated in the example.

Separately, the same storage test as described above, carried out on a sample prepared in the same manner by adding acrylic acid to the unsaturated Polyurethane resin solution obtained according to Example 2 was treated. The results obtained in this case are in Table IV is also shown for comparison.

4 0 9 8 2 0/1 053

When using acetic acid instead of acrylic acid were adversely affected the curing properties of the resin, and only products could be obtained whose properties were bad.

Table IV Number of days elapsed for gelled to form.

material

sample O Acid number 10 15th .20 Resinous
Solution of the
Example 1 less than 1 day .5 35 days 62 days 65 days Resinous
Solution of the
Example 2 Il 6 days 46 70 70 Resinous
Solution of the
Example 14 It 8th 25th 50 55 comparison '· ■ 5 15th 18th 33 2

409820/1 0 53

Claims (1)

Claims Process for the production of an unsaturated polyurethane resin, Containing 2 or more unsaturated snono-basic SMurer residues in its molecular structure, characterized in that that in the presence of a polymerizable vinyl monomer A) a di-esterified product of an epoxy compound, ent- containing a hydroxyl group _s whereby this product was obtained by reacting an epoxy compound, which has 2 epoxy groups in its molecular structure, but does not contain a hydroxyl group, with an unsaturated monobasic acid, with B) -a-diisocyanate compound in the presence or absence is from C) an oligopolyester glycol containing a saturated or unsaturated dibasic acid group ^ in a ratio of 0.2 to I ₅ O moles of the isocyanate group per each mole of the hydroxyl group, 2o) Process for the production of an unsaturated polyurethane resin Sj, containing 2 or very unsaturated snonobasic acid residues in its molecular structure, characterized in that that in the presence of a polymerizable vinyl " monomers A) containing a di-esterified product of an epoxy compound a hydroxyl group, this product being formed by reaction of an epoxy compound which has 2 epoxy groups in their molecular structure, but no hydroxyl group contains, was made with an unsaturated monobasic acid. 409820/10 53 235385t - 25 - ^; - ■ "■■■■ '■". -, ■ -.- - with B) a diisocyanate compound in the presence or Absence of . ^; "...:"'"""" ■■ ".-. ' - - '. _: - ^l ' - </ :: ■■. :. C) an oligopolyester glycol containing a desaturated or unsaturated dibasic acid soup, in a ratio of 0.2big -i _t Ö MoJIsocyan4tgruppen per mole of hydroxyl groups and η after completion of the reaction -D) «a monoalkyiester *? unsaturated dill fish Slure added to the reaction product 3.) The method according to any one of claims 1 or 2 _S, characterized in that the unsaturated monobasic: acid is an acid selected from the group consisting of AcryX and M 409820/10 53