JPS62223204A - Production of crosslinked polymer - 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 a crosslinked polymer and a method for producing the same. More specifically, this invention relates to acetoacetate and α
, relates to crosslinked polymer systems written as a result of reaction with b-unsaturated esters.

Several drawbacks have been experienced with current room temperature and thermoset compositions, particularly those formulated with melamine or urea formaldehyde resins. This is because during the curing cycle, ionic volatiles are generated, including free formaldehyde, but incyanate is highly
It has been observed that compositions containing these materials have undesirable side reactions when cured at room temperature, especially in the presence of moisture. Epoxy resin-containing compositions cure over a wide range of temperatures depending on the curing agent used. However, curing agents for epoxy resins are often very 111-sensitive and act as sensitizers in humans. Moreover, their external durability is unsatisfactory, so their use is generally limited to use as brimers.

This invention relates to a method for producing crosslinked polymers. The process of the invention involves transesterifying an alkyl acetoacetate with a polyhydroxy-functional monomer or polymer in the presence or absence of a catalyst, and transesterifying the acetoacetate-functional monomer or polymer thus formed with a polyfunctional α,β- and unsaturated esters in the presence of strong basic or organometallic catalysts. The invention also relates to crosslinked polymers produced by this method.

In accordance with the present invention, a crosslinked composition is provided which can be cured without undesirable side reactions, even though the drawbacks associated with other crosslinking systems are overcome. At R temperature, satisfactory curing can be achieved in the shortest time. The quality of coatings made using the crosslinked Mt compositions of this invention is comparable to the quality of current primer coatings or high durability topcoach inks. When the crosslinking composition of the present invention is used as a coating composition, it has the advantage of meeting current US Environmental Protection Agency (1:P8) VOC (volatile organic compound) regulations. Coatings or films made using the crosslinked compositions of this invention exhibit excellent adhesion, excellent solvent resistance, excellent gloss retention, excellent flexibility, and excellent hardness. These properties are based on this emission 11
When the composition of 1 is coated on various substrates, such as chromated aluminum, zinc, iron and phosphated steel, and various plastics such as polyamide, polycarbonate, ABS, and polyphenylene oxide. can get.

Polymers made from the Mlah of this invention are useful as coatings for high-grade cabinets, automotive top coats, primers, aluminum extrusions, office furniture, and wood products. The industry that uses such coatings has needed a high quality, low temperature cure coating that meets EPA vOC regulations. This invention does not meet these needs.

This product I provides a method for preparing acetoacetate and the α,β-unsaturated ester component for the polymer as well as the crosslinked polymer itself.

The method for producing crosslinked polymers of this invention comprises transesterifying an alkyl acetoacetate with a polyhydroxy-functional monomer or polyhydroxy-functional polymer in the presence or absence of a catalyst, and the acetoacetate-functional monomer or polymer thus formed. and an α,β-unsaturated ester to form a strong Ii! Other embodiments of the invention include reacting in the presence of a base catalyst or an organometallic catalyst.

Films produced according to this invention have excellent hardness,
Exhibits excellent solvent resistance, excellent adhesion, excellent Of flexibility and excellent gloss retention after accelerated exposure. Advantageously, coatings using this new system can be formulated with extremely low amounts of volatile organic solvents that meet EPA regulations.

One reaction that is relevant to one embodiment of the method of this invention is what is known as the Mikel reaction. Michael reaction is lccbanism and 5structure
in Organic Cbelstry” (
E, S, Gould, p, Koku2-394
; Holt Reinhard and Inston, New York
, 1959). Generally, in the Mickle reaction, acetoacetic acid forms a carbanion in the presence of a strong ill group. The carbanion then reacts with an α,β-unsaturated carbonyl compound.

The reaction can be carried out with acetoacetate.

Advantageously and preferably, an excess of i,i of the acetoacetic acid functional compound is used to ensure complete reaction with the polyα,β-unsaturated material. By using an excess of chemical sterilization to ensure complete reaction, coach inks made from this composition may take on an undesirable yellow color and reduce the durability of the external coating. Prevented. The ratio of polyacetoacetic acid functional compound to polyα,β-unsaturated crosslinking compound is from 0.60 to 1.60 to 1.60 to 0.60, more preferably from about 1.0:1.11 to about 1.0. :0.8
It is.

In a first step of one embodiment of the method of this invention.

Polyacetoacetate materials are obtained by transesterification with polymers or polymers. Suitable alkyl monofunctional ethyl acetoacetates for transesterification are methyl acetoacetate, ethyl acetoacetate, isopropyl acetoacetate, butyl acetoacetate, 1-butyl acetoacetate, methylbenzyl acetoacetate and dodecyl acetoacetate.

Suitable polyhydroxy-functional monomers and polymers include, for example, 1,6-hexanediol, neopentyl glycol, ethylene glycol, cyclohexalinemethanol,
Diethylene glycol, 1,4-butanediol, trimethylolpronone, trimethylolethane, glycerin, hydroxy-functional acrylic resin (α-methylstyrene/E-caprolactone (Union Calcium)
3 of hydroxyethyl acrylate/2-ethylhexyl acrylate modified with ONF +00 (QR Trademark)
5155/10 weight mixture, and a styrene/allylic alcohol copolymer (Monosand IIJ-100).

Additionally, acetoacetic acid functional ester materials suitable for use herein include reaction products of alkyl monofunctional acetoacetic acids with epoxy resins and their esters, oil-free polyesters, and alkyd or acrylic resins. A suitable epoxy resin is EP reprinted by Shell Chemical Co.
Something like ON +001 (registered trademark).
Examples of acetoacetic acid functional alkyds include tall oil fatty acids,
By reacting benzoic acid, phthalic anhydride and pentaerythritol, the intermediate is 1! I1 can then be obtained by reacting this intermediate with an alkyl monofunctional acetoacetic acid. If a catalyst is used in the transesterification step of the process of this invention, suitable catalysts include methylsulfonic acid, para-toluenesulfonic acid.

Acetoacetate-functional materials thus include acetoacetate-functional resins and oligomers having two or more functionalities.

Examples of polyalpha,beta-unsaturated materials useful for this invention include polyfunctional methacrylate, acrylate, cinnamate and crotonate functional oligomers and polymers and malate and itaconate modified resins. Suitable polyα,β-unsaturated materials include 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, maleic acid-modified polyesters, itaconic acid-modified polyesters, as well as acrylics, crotonic acid-modified acrylics and Mention may be made of trimethylolpropane tricinnamate. An example of a maleic acid-modified polyester has a molar ratio of maleic anhydride to polypropylene glycol of 1.0/1.1, and is reduced to a 60% non-volatile substance in methyl amyl ketone. Suitable rotonic acid modified acrylic is glycidyl methacrylate (GMA)
/Butyl acrylate (BA)/Methyl methacrylate (M
It is obtained by reacting crotonic acid with an acrylic resin containing a mixture of 25/25/20/30 (by weight) of M8)/styrene with a non-volatile content of 60% in xylene. Acrylate functional acrylic resin is a 25/25 mixture of acrylic acid and glycidyl methacrylate/butyl acrylate/styrene/methyl methacrylate.
/30120 (weight ratio) It can be obtained by reacting with a copolymer.

Among the unsaturated compounds mentioned above, crotonate and itaconate compounds are preferred. The compound exhibiting the most advantageous curing reaction is represented by the following formula.

-CH=C-C-0- where R is independently H, methyl or -C-0,0 +1' is independently Hl-CH2-C-Q or -C1
13 is shown.

The second step of the process of this invention involves reacting the acetocholic acid functional ester material in the presence of a poly alpha, beta unsaturated crosslinking agent or catalyst. In one embodiment of this invention, the catalyst is preferably a strong base. Suitable catalysts of this type include sodium alcoholade, potassium hydroxide, tetrabutylammonium hydroxide, dimethylethanolamine, ammonia and triethylamine. The amount of strong salt employed in this embodiment of the process of the invention is, for example, from about O.SX to about 5% based on total resin solids. The star of the catalyst and the type of catalyst are determined by the reactivity of the acetoacetate group with α,β-unsaturated substances,
It depends on whether air drying or baking equipment is used, and the time and temperature of the baking cycle.

Preferred organometallic compounds include lead, cobalt, manganese, zinc, calcium, iron, zirconium, lanthanum,
2-ethylhexanoate and 2-ethyl ocnaceate of chromium, potassium or vanacium; lead, cobalt, manganese, zinc, calcium,
Mention may be made of naphthenates of iron, potassium or cerium: as well as neodecanoates, isononanoates, heptanoates of calcium, cobalt, lead, manganese, zinc, zirconium or iron and mixtures thereof. Also, manganese (If), (II+), Kobal) - (1
1), (IV) Acetoacetonates of chromium, lead, potassium, etc. and mixtures thereof may be mentioned.

The amount of catalyst used in the process of this invention may vary, for example, from about 0.20 to about o, aox, based on the weight of total carrier solids.
, preferably in the range from about o,onx to 0.25K. The selection and type of catalyst are acetoacetic acid I% 1 group and α
, reactivity with β-unsaturated materials, whether air drying or baking equipment is used, and baking cycles can be performed. Advantageously, the curing step is carried out at elevated temperatures. This is because conductive enamels and coatings can be made from this IJI polymer embodiment which, when carried out at elevated temperatures, provide the most satisfactory curing in a short period of time. Such enamels and coatings can be rendered electrically conductive by incorporating a quantity of electrically conductive filler such as carbon black.

1 real example The following non-limiting examples illustrate the invention.

Examples 1 to 7 illustrate acetoacetic acid functional polymers and monomers and methods of making them.

Example 2 Thermometer, inert gas distribution pipe, valley distillation receiver and water a
In a 3 g reactor equipped with a
of sodium methoxide or para-toluenesulfonic acid. This mixture was heated under a light nitrogen blanket for 92 hours.
Heated to ℃. Ethanol began to distill at this temperature. The temperature increased as ethanol was removed, reaching a maximum of 135°C. The remaining traces of 1 hjL of ethanol were removed by replacing the nitrogen blanket with a nitrogen stream. Total ethanol recovered was 95% of theory. The product, trimethylolpropane triacetoacetate, is
The Gardner-Holtz viscosity in 100% It volatiles was Z6◆, and the equivalent weight was 129.

The raw material hexanediol diacetoacetate was prepared by the method described in Example 1. 622 g of 1,6-hexanediol in the absence of transesterification catalyst or in the presence of 2 g of para-toluenesulfonic acid.

1: Reacted with 176 g of ethyl acetoacetate. The product obtained had a Gardner-Holch viscosity of A at 100 z of non-volatile material and an equivalent weight of 14 oz.

[An acetoacetate ester of a styrene/allylic alcohol copolymer (Monosanto nJ-100) with hydroxyl groups J11 or 300+IS was prepared in the same manner as in Example 1. After the acetoacetate was prepared, it was reduced to 70% non-volatile material in a 67/3:lk mixture of xylene/methyl isobutyl ketone. The obtained acetoacetate z6+ had a viscosity of 400 equivalents on a solid basis.

960 g of tall oil fatty acids and 1599 g of EPON +001® from Shell Chemical Co. were reacted in a 5-liter reaction flask equipped with a stirrer, water condenser, valley distillation receiver, thermometer and nitrogen spasitube. I let it happen. Heat the reactants to 200-210°C under nitrogen flow.

It was held at this temperature until acid number was below 10.

The obtained epoxyester was cooled to 145°C, and 1003
g of ethyl acetobutyrate and 3 g of para-toluenesulfonic acid were added. Ethyl acetoacetate was transesterified and ethanol was recovered as in Example 1. This resin, concentrated at 8 oz non-volatile in methyl amyl ketone, is
It had a viscosity of 6+ and an equivalent weight of 514 on a solids basis.

903 g neopentyl glycol, 180 g trimethylolethane, into a 5-piece reaction flask equipped with a steam fraction concentrator, thermometer, stirrer, and nitrogen sparge tube.
264 g of adipic acid, + 206 g of isophthalic acid and 3 g of dibutyltin oxide were charged. reduce the temperature
/ The temperature was raised to 230℃. The resin was treated with 601 non-volatile in xylene to a rancidity of less than 10 and a U-v viscosity.

Polyester box 1 hour
was reduced in methyl amyl ketone. At 1300C 400g of ethyl acetoacetate and 3g of dibutylsulfur oxide or 3g of para-toluenesulfonic acid were added to the polyester. The steam concentrator was replaced with a water concentrator and Halley distillation receiver.

Ethanol was removed as in Example 1. Acetoacetate functional polyester is 26+ with 86% non-volatile content
The equivalent weight was 932 on a solids basis.

扛j 537g of tall oil fatty acid, 216g of benzoic acid,
An acetoacetic acid functional alkyd was made by first reacting 484 g of phthalic anhydride with 454 g of pentaerythritol. This resin was made using the equipment described in Example 1. 9 to help remove water of esterification
0 g of xylene was added. The resin was heated to 15-20 acid number and 40% non-volatiles in xylene to give an E-F viscosity. The maximum temperature at this stage was 200°C.

The resin was then cooled to 150°C and treated with 1200g ethyl amyl ketone, 307g ethyl acetoacetate and 2.0g
of para-toluenesulfonic acid was added. Ethyl acetoacetate was transesterified with the alkyd. Ethanol was removed via the receptor. The procedure was similar to Example 1.

The resulting modified alkyd was 6 oz non-volatile, had a viscosity of Y-Z, and had an equivalent weight of 861 on a solids basis.

An acetoacetate-functional acrylic was created by first creating a hydroxy-functional acrylic. This consists of 172g of styrene, 5112g of butyl methacrylate, and 3
This was done by reacting 43 g of butyl acrylate, 570 g of hydroxyethyl acrylate and 116 g of cumene hydroperoxide in refluxing methyl amyl ketone (1085 g) and cumene hydroperoxide (28 g). 6 reactions in which monomer and catalyst were added simultaneously and continuously over 4 hours to an i-stream solvent.
The reaction was carried out in a 5-piece reactor equipped with a stirrer, addition funnel, thermometer, Halley distillation receiver and water concentrator. After adding the salt, heat the resin at 3±3°C until its viscosity reaches D-E.
The reflux temperature was maintained at .

The resulting acrylic resin was then cooled to 100° C. and at this temperature 640 g of ethyl acetoacetate and 4 g of para-toluenesulfonic acid were added. The transesterification byproduct, ethanol, was removed via Hallei's receptor membrane as described in Example 1. The final product was 5% in methyl amyl ketone.
It had a viscosity of D-1 at 8% non-volatile matter, and the h content was 41 (1) on a solid basis.

Examples 8-1B Examples 8-18 illustrate paint coach inks made from the acetoacetic acid functional polymers of Examples 1-7.

Example 8 A glossy white enamel was formulated with a PvC content of 16% and a solids volume of 52%.

The acetoacetic acid functional ester material prepared in Example 1 is α,
It was reacted with an acrylate-functional acrylic resin as a β-unsaturated crosslinker. Reacted with GMA/acrylic. The reaction was catalyzed with 2% tetraphthylammonium hydroxide based on the carrier solids content. The resulting white enamel was then evaluated and found to have the following properties:

Gloss 94/60', 60/200 Pencil hardness 2H Solvent resistance 100+MEK double friction
Rubs) Crosshatch Adhesion Tape 100% retention old glossy white enamel was formulated with % HtIS containing PvC and 52% solid JA. This system can be colored using commercially available coloring systems.

The acetoacetic acid functional ester material prepared in Example 2 was
A stoichiometric amount of the acrylate-functional acrylic resin of Example 7 was reacted as an α,β-unsaturated crosslinker. The reaction was baked for 30 minutes with 2% t-1-butylammonium hydroxy to solids content. The resulting white enamel was then evaluated and found to have the following properties:

Gloss 98/60°, 77/20' Pencil Hardness H-2H Solvent Resistance 100◆MEK Double Friction Crosshatch 472 100% Tape Retention Made of cold rolled steel treated with a portion of the above glossy white enamel The white enamel obtained was then evaluated and had the following properties:

Gloss 94/60°, 82/20' Pencil Hardness H Solvent Resistance 50 EK Double Friction Crosshatch Adhesion 10 Tapes 2 Holding Example 10 Conductive dark clay epoxy ester primer for metals and plastics was applied as follows. I made it. This coach ink contains 21.80 active PVC (containing carbon black and tin oxide) and 42.9% total PV.
It was formulated in C.

The acetoacetic acid functional ester material prepared in Example 4 was
It was reacted with a stoichiometric amount of III with trimerthousandolpropane triacrylate as α,β unsaturated crosslinker.

The reaction was carried out in the presence of a 2% tetrabutylammonium hydroxide catalyst based on the solid support 14. After treatment, the resulting white enamel was evaluated and found to have the following properties: Was.

Pencil hardness Initial B ÷, H after 72 hours Solvent resistance
After initially 35 anal K and 2 m office rub and 72 hours later 50◆, the resulting white enamel was evaluated and found to have the following properties.

Pencil hardness Initial H17 2H after 2 hours Solvent resistance Initial 60 MEK Double PI! Rub, 100 after 72 hours
+ Example 11 Glossy white enamel with PVC content 16z.

and solid objects were formulated.

The acetoacetic acid functional ester material prepared in Example 1 is α,
Two different stoichiometric amounts were reacted with acrylate-functionalized acrylic resin as a β-unsaturated crosslinker. The two reaction products were cured to produce two glossy white polyester enamels.

This was baked and evaluated as follows.

, (a) the first crosslinked polymer is an acetoacetate:
A 1:0.80 stoichiometric ratio of acrylate functional crosslinker was baked for minutes in the presence of 2% tetrabutylammonium hydroxide catalyst based on the solids content of the support. Enamels made from this polymer were then evaluated and found to have the following properties:

Gloss 95/600.85/20° Pencil Hardness F-H Solvent Resistance 50 to ME Double Friction Crosshatch Adhesive Tape 10oz Hold I, ν(b)th λ Crosslinked Polymer is Acetoacetate: Acrylate Functional Crosslinker The ratio of 1:0.60 is 1
The enamel made from this polymer was then evaluated and had the following properties:

Gloss 92/60°, 74/20° Pencil hardness H Solvent resistance 501EK Double friction Crosshatch attachment 100% tape retention example 12 Glossy white enamel with PvC content + aX.

and a solid volume of 44×.

The acetoacetic acid functional ester material prepared in Example 3 was
It was reacted with trimethylolpropane triacrylate as an α,β unsaturated crosslinking agent in a stoichiometric amount of 1:1.

The reaction was carried out in the presence of a 2% tetrabutylammonium hydroxide catalyst based on the solids content of the support.

The cross-linked polymer thus produced is air-dried and smoked.
It was then cured for 96 hours on a substrate consisting of treated cold rolled steel.

The resulting white enamel was then evaluated and found to have the following properties:

Gloss 92/60°, 74/20' Pencil hardness 2
H Solvent resistance 50 MEK double friction, 68 hours li!
? , 100 MEK double coated, 96 hour crosshatched tape 100% retention Example 13 Glossy white enamel with PVC content of 2 oz.

and solid objects J! 145,61.

The acetoacetate-functionalized Nisdel prepared in Example 2 was α,
It was reacted with a crotonate-functional acrylic as a β-unsaturated crosslinker at a stoichiometric amount of I: 0.80. The reaction was carried out in the presence of a tetrabutylammonium hydroxide catalyst of 5% based on the solids content of the phase. The crosslinking agent is also 60% non-volatile in xylene, GM^/B
8/S/HeM8/Kurohenm (weight ratio 21.7/21.
7/26-0/17.4/I:1.2). After being produced in this way, the resulting white enamel was evaluated and found to have the following properties:

Gloss 88/611', 62/200 pencil hardness F
-H Solvent Resistance 50 ME Double Agency Rubbing Loss Hatching Tape 100z Retention Example 14 Glossy white enamel with PvC content of 20% and solid object J! i4s, sx were formulated.

The acetoacetic acid functional ester prepared in Example 7 was α,
The 0 reaction with the crotonate-functional acrylic of Example 7 as a β-unsaturated crosslinker at a stoichiometry of l:0.80 was performed using 5% tetrabutylammonium hydroxide based on the solids content of the tl1 body. It was carried out in the presence of a catalyst. After being produced in this way, the resulting white enamel was evaluated and found to have the following properties:

Gloss 94/60', 116/20° Pencil hardness H! Solvent Resistance 50 MEK Double Friction Crosshatch Adhesive Tape l fl O! Retention Example 15 A glossy white enamel was formulated with a PVC content of 3.27% and a solid body M of 51%.

The acetoacetic acid functional ester prepared in Example 7 was α,
It was reacted with a methacrylate-functional acrylic resin as a β-unsaturated crosslinker at a chemical pressure of 0.80. The reaction was carried out in the presence of 5% tetraphthylammonium hydroxide catalyst based on the solids content of the support. The crosslinking agent is also a non-volatile substance in xylene 60! in,
GM 8 to MAA/BA/SUM 8 to weight ratio 21.7/
21.7/26.0/17.4/13.2). Don't make it like this. after that,
The resulting enamel was evaluated and had the following properties:

Gloss 8'l/[ioo, 82/20O pencil r+ degree
B+ Solvent resistance Initial, 17 MEK Double rub, - After, 25 MEK, unsolvated crosshatch adhesive Tape 100% retention Example 16 Clear acrylic enamel solid volume 45,6! It was formulated with

The acetoacetic acid ester produced in Example 2 was α,
Example 1 as a β-unsaturated crosslinker was reacted with methacrylate-functional acrylic of Example 15 in a stoichiometric amount of I: 0.80. The reaction was carried out in the presence of 5% tetraphthylammonium hydroxide catalyst based on the solids content of the support. The cross-linked polymer thus produced is then processed into cold rolls. The resulting white enamel was then evaluated and found to have the following properties:

Pencil Hardness H Solvent Resistance 50 MF, K Double Rub Example 17 A glossy white enamel was formulated with PvC content of 18 $ and solids volume of 50%.

The acetoacetic fE ester produced in Example 1 was
, reacted with itaconate-functional acrylic resin as a β-unsaturated crosslinker. Itaconate polyester is made by combining itaconic acid and propylene glycol in a ratio of 1:1. It was produced by reacting in a molar ratio of 1. The reaction was carried out in the presence of 2% tetrabutylammonium hydroxide catalyst for a total solids content of 111 bodies. It was created in this way. The resulting enamel was then evaluated and found to have the following properties:

Gloss 90/60°, 72/20°Pencil Hardness 11B Solvent Resistance 50MF, K Double Friction Crosshatch Adhesion Tape 100% Retention Example Same as Example 1 except that no tetratstylammonium hydroxide catalyst was used. A glossy white enamel was produced in a similar manner. The coach ink was sprayed onto a panel of cold-treated rolled steel.

After air drying for 30 minutes at room temperature, the panels were inverted in an 8 ounce open container of dimethylaminoethanol.

In this arrangement, part of the film was exposed to the amine vapor, but part of the film was not. After being left in this state for 12 hours, curability was evaluated by measuring solvent resistance to methyl ethyl ketone. The results of the evaluation were as follows.

Unexposed Film O double rub MEK-film solvated.

EXPOSED FILM EXAMPLE 19 WHERE A FILM WAS NOT SOLVATED IN THE ME OF 25 DOUBLE RUBS This example relates to the evaluation of additional unsaturated materials suitable for use in the method of making crosslinked polymers of this invention.

Trimethylolpropane triacetoacetate, seed/
It was used to evaluate the reaction with carbon-carbon unsaturation in the form of l. The acetoacetate ester and the unsaturated substance are equivalent to 1. 1 was mixed. The mixture was then evaluated for 25% alcoholic potassium hydroxide. Gelation is when a mixture transitions from a liquid state to a solid or semi-solid state.
α.

Physical changes that occur in β-unsaturated ester mixtures.

The results of these tests are shown in Table 1.

Table 1 (1) Trimethylolpropane triacrylate gelling Lrζ (2) Trimethylolpropane trimethacrylate gelling (3) Maleic acid modified polyester (a) Gelling! .

(4) Itaconate-modified polyester (b) Gelled (5) Crotonic acid-modified acrylic (C) Gelled L
/C(6) Trimethylolpropane tricinnamate γ
(a) Maleic anhydride/propylene glycol (1
,0/1.1 molar ratio) (b) Itaconic acid/propylene glycol (1,0/1.1 molar ratio) reduced to the non-volatile substance 6H in methyl amyl ketone.
1.1 molar ratio) (C) GMA/DA/S/MMA/crotonic acid (21
, 7/21.7/26.0/17.4/13.2 weight ratio), 60% non-volatile material in xylene. This shows that it reacts with α, β-unsaturated ester substances to form crosslinks.

Examples 20-23 illustrate coatings made from the acetoacetic acid functional polymers of Examples 1-7 in the presence of organometallic catalysts.

Example 10 A stock mixture of hexanediol thiacetoacetate from Example 2 and acrylate-functional acrylic resin was made. Acrylate functional acrylic resin is 25/25/
It was prepared by reacting glycidyl methacrylate functional acrylic with acrylic acid containing glycidyl methacrylate/butyl acrylate/styrene/methyl methacrylate in an ffi ratio of 30/20. The equivalent weight of acrylate with 1001 non-volatile material on a gLfltl basis was 640. The stoichiometric ratio of the reactants was 1.0=15 to 30 minutes on a solid basis. The obtained film had the properties shown in Table 2.

F　　　　　　　　　　　　　　　　.

Ro Ro NNC%I e%I C%J
FJ IN 81%1w ==e: :l: IJ
+Nz + zl ro 0 ro
The following examples demonstrate the curing and film properties of glossy black enamel films cured with several different metal carboxylates using the coating system of Example 8.

Example 21 A glossy black enamel coating was formulated with the acetoacetate/acrylate functional mixture obtained in Example 8.

Coach ink was formulated with an active PvC of 3.8z and a volume of 52 solids. Test results for various metal carboxylates coated with 0.06X gold based on carrier solids are shown in Table 3.

Example 22 A stock mixture of hexanediol diacetoacetate and crotonate-functional acrylic was prepared by the method described in Section 2, which was then reacted with a crotonate-functional acrylic resin as a poly alpha, beta-unsaturated ester crosslinker. The stoichiometric ratio of reactants is 1.0:1 on a solid basis
．． It is 0. Crotonate-functional acrylic resin is a combination of crotonic acid and glycidyl methacrylate/butyl acrylate/styrene/methyl methacrylate copolymer (25/
25/:10/20 Tl Q ratio).

Control sample (a) had no catalyst added. The catalysts successfully used in samples (b), (c), and (d) of the present invention shown below were lithium neodecanoate, manganese octoate, and vanadium octoate, respectively.

The properties of are shown in Table 4.

It has also been found that pot life or stability can be extended from hours to weeks by adding oxime compounds to the system. Examples of oxime compounds are methyl ethyl ketoxime and butyraldoxime. The concentration of the oxime compound is 0.05 to 0.0, based on the carrier solids.
It is 60X. The following examples illustrate pot life extension and hardening to film properties.

Example 23 Same as Example 8 using acetoacetic crosslinker and acrylate functional resin. One sample was mixed with manganese octoate (4'0
The catalyst was catalyzed using 0.12×gold Ws (based on body solids). Second
A sample of 1 was catalyzed similarly except that 0.60$ of methyl ethyl ketoxime, based on support solids, was added. The results are shown in Table 5.

Stability is the time from catalysis with an organometallic compound to gelation.

Claims (23)

[Claims] (1) (a) transesterifying a monofunctional alkyl acetoacetate with a polyhydroxy-functional monomer or polyhydroxy-functional polymer to produce a polyacetoacetate-functional monomer or polymer; and (b) converting the polyacetoacetate-functional monomer or polymer into reacting the poly α, β-unsaturated ester with crotonic acid, acrylic acid, methacrylic acid in the presence of a strong basic catalyst capable of initiating the reaction. , maleic acid or itaconic acid with polyhydroxy- or epoxy-functional monomers or polymers or mixtures thereof. . (2) The monofunctional alkyl acetoacetate is methyl acetoacetate or ethyl acetoacetate.
The method described in section. (3) The polyhydroxy functional monomer or polyhydroxy functional polymer includes 1,6-hexanediol, diethylene glycol, 1,4-butanediol, neopentyl glycol, ethylene glycol, cyclohexalinemethanol, trimethylolpropane, trimethylolethane, 2. The method of claim 1, wherein the resin is selected from the group consisting of glycerin, epoxy resins, epoxy esters, oil-free polyester resins, alkyd resins, acrylic resins and styrene/allylic alcohol copolymers and mixtures thereof. (4) The strong base is selected from lithium hydroxide, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylethanolamine, ammonia, triethylamine and mixtures thereof. A method according to claim 1 selected from the group consisting of: (5) The poly α,β-unsaturated ester is selected from the group consisting of 1,6-hexanediol diacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, and trimethylolpropane tricinnamate, and mixtures thereof. The method according to claim 1. (6) The poly α,β-unsaturated ester consists of maleic acid-modified acrylic and polyester resins; itaconic acid-modified acrylic and polyester resins; acrylate-, methacrylate-, and crotonate-modified acrylic, polyester, and alkyd resins; and mixtures thereof. A method according to claim 1 selected from the group. 7. The method of claim 1, wherein in step (b) carbon black particles are added in an amount sufficient to render the final crosslinked polymer electrically conductive. (8) The ratio of the polyacetoacetic acid functional monomer or polymer to the poly α,β-unsaturated ester is about 0.50.
:1.50 to 1.50:0.50. (9) Acetoacetic acid functional monomer or polymer and α,β-
and an unsaturated ester in the presence of a strong base catalyst capable of initiating a microreaction,
A process for producing crosslinked polymers, wherein the α,β-unsaturated ester is prepared by reacting crotonic acid, maleic acid or itaconic acid with a polyhydroxy or epoxy functional monomer or polymer or a mixture thereof. (10) reacting trimethylolpropane triacetoacetate with an α,β-unsaturated ester in the presence of a strong base catalyst capable of initiating a microreaction, wherein the α,β-unsaturated ester is , a method for producing a crosslinked polymer made by reacting acrylic acid with glycidyl methacrylate, butyl acrylate, styrene and methyl methacrylate. (11) (a) transesterifying a monofunctional alkyl acetoacetate with a polyhydroxy-functional monomer or polyhydroxy-functional polymer to produce a polyacetoacetate-functional monomer or polymer; and (b) transesterifying the polyacetoacetate-functional monomer or polymer with an organic reacting the polyα,β-unsaturated ester with crotonic acid, acrylic acid, methacrylic acid, maleic acid or itaconic acid and polyhydroxy or A method for producing crosslinked polymers from acetoacetic esters and poly alpha, beta-unsaturated esters, which are esters with epoxy functional monomers or polymers. (12) The method according to claim 11, wherein the monofunctional alkyl acetoacetate is methyl acetoacetate or ethyl acetoacetate. (13) The polyhydroxy functional monomer or polyhydroxy functional polymer includes 1,6-hexanediol, diethylene glycol, 1,4-butanediol, neopentyl glycol, ethylene glycol, cyclohexalinemethanol, trimethylolpropane, trimethylolethane, 12. The method of claim 11, wherein the resin is selected from the group consisting of glycerin, epoxy resins, epoxy esters, oil-free polyester resins, alkyd resins, acrylic resins, and styrene/allylic alcohol copolymers. (14) The poly α,β-unsaturated ester is 1,6-
12. The method of claim 11, wherein the method is selected from the group consisting of hexanediol diacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate and trimethylolpropane tricinnamate, and mixtures thereof. (15) The poly α,β-unsaturated ester is selected from the group consisting of maleic acid-modified acrylic and polyester resins; itaconic acid-modified acrylic and polyester resins; acrylate, methacrylate, and crotonate-modified acrylic, polyester, and alkyd resins. The method according to claim 11. (16) The organometallic compound is (a) 2-ethylhexanoate or octoate of lead, cobalt, manganese, zinc, calcium, iron, zirconium, lanthanum, chromium, potassium or vanadium; (b) lead, cobalt, manganese; , naphthenates of zinc, calcium, iron, potassium or cerium; (c) talates of lead, cobalt, manganese, calcium or iron; (d) neodecanoates of calcium, cobalt, manganese, lead, zinc, zirconium or iron; (e) carboxylates selected from the group consisting of isononanoates of calcium, cobalt, lead, manganese, zinc, zirconium or iron; and (f) heptanoates of calcium, cobalt, lead, manganese, zinc, zirconium or iron; and mixtures thereof. 12. The method according to claim 11. (17) The method according to claim 11, wherein the organometallic compound is an acetoacetonate of manganese, cobalt, chromium, lead, calcium, cerium, or iron, or a mixture thereof. 18. The method of claim 11, wherein the organometallic compound catalyst is present in an amount sufficient to provide 0.02 to 0.08% metal based on total rejection solids. (19) The ratio of the polyacetoacetic acid functional monomer or polymer to the poly α,β-unsaturated ester is about 0.5.
12. The method according to claim 11, wherein the ratio is from 0:1.50 to 1.50:0.50. (20) the polyacetoacetic acid functional monomer or polymer is mixed with the poly α,β-unsaturated ester in the coexistence of a pot life extender selected from the group consisting of methyl ethyl ketoxime and butyraldoxime; 12. The method of claim 11, wherein is present from 0.05 to 0.50% based on total carrier solids. (21) polyacetoacetic acid functional monomer or polymer,
a process stage for reacting polyα,β-unsaturated esters in the presence of organometallic compounds, wherein the polyα,β-unsaturated esters are reacted with crotonic acid, acrylic acid, methacrylic acid, maleic acid or itaconic acid and polyhydroxy or an ester with an epoxy functional monomer or polymer. (22) polyacetoacetic acid functional monomer or polymer,
reacting the polyα,β-unsaturated ester with crotonic acid, acrylic acid, methacrylic acid, maleic acid or itaconic acid and polyhydroxy or A method for producing crosslinked polymers that are esters with epoxy functional monomers or polymers. (23) The method according to claim 22, wherein the metal compound is a manganese compound.