DE1770073A1 - Process for making an improved resin binder for stoving enamels - Google Patents

Description

DESCRIPTION of the patent application of the N.V. Chemical industry Synres

Seat

Concerning Hoek van Holland (Netherlands).

Process for making an improved resin binder for stoving enamels.

The invention relates to a method for producing an improved resin binder for stoving enamels, using a polyether glycol of the general formula | (Ho (R-O) H, in which R is an alkyl radical with at least 3 carbon atoms represents and n ^ 2 with the double molar amount of a monoolefinic unsaturated dicarboxylic acid or the anhydride thereof esterified, the dicarboxylic acid obtained is esterified with the double molar amount of a glycidyl ester of an α, α dialkyl .-Substituted alkanecarboxylic acid of the general formula

R ₁
1

- COOCH ₂ - CH CH ₂ , in the R _{.,, R 2} and R,

109839/1366

represent saturated alkyl radicals and the obtained unsaturated Diester with a mono-olefinically unsaturated one polymerizable compound copolymerized.

The mono-olofinic used for esterification -unsaturated dicarboxylic acid or its Anh / drid can partially- " wisely be replaced by a saturated dicarboxylic acid or its anhydride. This can reduce the degree of unsaturation (the functionality) of the monomer and thus the branching of the copolymer are regulated.

The polyether glycol used is preferably a polyether glycol of the general formula HO (RC) H, in which R is the group -C ₄ H ₈ and n = 10-20.

As a glycidyl ester of an α, α-dialkyl-substituted one Alkane carboxylic acid is preferably Cardura-E.

Oardura-E is given with the general formula

R ₁ O

R ₂ -C- COOH ₂ - CH CH ₂ , in which R ₁ , R ₂ and R ₅

represent saturated alkyl radicals B, where the total number Carbon atoms of the acidic part of compound 9-11 amounts to.

The thermoplastic copolymerizate obtained mixed in per se known V ^r else with a thermosetting resin which resin can react with this Kopolymcrisat to form a three-dimensional cross-linking, such as a melamine resin, as baking finishes are obtained,

109839/1366

BATH ORIGINAL

where lc lic Fi In υ show that they are very resistant to chemicals such as alkalis. Detergents \ χ: Λ Zf ¹ ;. + - ⁴ "-? -

This favorable property becomes the ste.rischen hindrance attributed to the ester group already present in small numbers in the polymer Ethur bridges, e.g. with a melamine resin, result of course L-inu good chemical resistance.

The specialty of the present resins is that they M

besides an excellent chemical resistance also, excellent * - have mechanical properties such as hardness, Elasticity and blow ajiti - it. These last properties are attributed to the presence of the polyether glycol.

As examples of meno-oiefinically unsaturated dicarboxylic acids, to the manuf. The process of cloning in consideration, be maleic acid, fume, acid, etc. called.

As a saturated dicarboxylic acid or its anhydride l-canr. Phthalic anhydride adipic acid, succinic acid or Succinic anhydride can be used.

Vorzurgswcise the Säureanh ^ anhydride used \ <oil will be asseabgespaltet in this case at the reaction no '''The reaction temperature may remain below 200 ⁰ C, which reduces the possibility of side reactions.

As mono-olefinically unsaturated monomers for copolymerization with the established connection are mentioned; Styrene, vinyl toluene, acrylates, methacrylates, maleates,

1 0 9 8 3 S / 1 3 6 6 bad

Fumarates, vinyl esters of "versatic acid" etc.

When copolymerizing it should be remembered that ο. It is necessary to use a small amount of an unsaturated Copolymerize monocarboxylic acid, such as 2-6% by weight acrylic acid, Methacrylic acid, or crotons ^ acid, making the The acid number of the copolymer is not more than 40. The carboxyl groups are then present in the copolymer, Fe the one for the closing reaction with the thermosetting Resin are required.

Next, "it is noted that even a verhältnisinässig _o Eringer content of the monomer produced exerts a favorable influence on the properties of the baked paint film in the final copolymerizate. In general sufficient, a content of 10-30 wt. ^ Of the monomer prepared in copolymerizate, said Content when replacing part of the unsaturated dicarboxylic acid with a saturated dicarboxylic acid can be higher.

Suitable copolymer ⁶ may be mentioned; a copolymer of: 40 - 75 wt. # styrene, 10 - 20 wt. $ acrylate, 2-6 wt. Eeth.ncryläure and 10-30 Gew. ^ Of the monomer produced; as well as a copolymer of: 66% by weight of styrene, 15% by weight, ew. 2-ethylhoxylacrylate, 6% by weight of methacrylic acid and 13% by weight of the monomer produced. The monomer becomes multistage in a simple manner

109832/1366 bad original

manufactured. First, a dicarboxylic acid from 1 mol Polyether glycol and 2 moles of unsaturated dicarboxylic acid anhydride manufactured. The reaction takes place at 120-110 ° C complete and is exothermic. When the heat development ends the reaction is complete. The temperature of the dicarboxylic acid formed is now brought to 170-175 C, whereupon 2 moles of glycidyl ester are slowly added. This reaction is also exothermic. Once all the glycidyl ester has been added, the acid number is determined. This should be a maximum of 5.

The copolymerization takes place in solution with a peroxide as a catalyst and optionally a chain transfer agent, like lauryl mercaptan. Will the monomer peroxide mixture Over a longer period, e.g. 2-3 hours added to the boiling L'öschuagsiaittel (mixture), needs you are not a chain transfer agent. The amount of excipients will be chosen so »that the solids content at the end of the copolymerization 50-75 Gew.ιζ is.

Preferably, butanol and xylene with a monomer concentration of 50% by weight are copolymerized in a mixture of equal parts by weight. . With 3 wt $ di ~ tert, -J ^ utylperöxyd as a catalyst and 0.8 "ew $ Laurylmemercaptan (based the total weight of the monomers) is 7 hours at the boiling point kopolymorisiert. (118-122 ⁰ C).

109839/1366

The copolymerization can be carried out on the basis of solids guhaltbe ^ ticinungon dus reaction mixtures ::; follow. The reaction is ended when this Fcctctoffgohalt enigütens is 50, ·.

For the production of Exnbrennlaci.cn the are producedon ! Copolymers with ._in_m thermo-curing resin mixed with it to form a three-dimensional en Networking can respond. Such resins are: Melamine resins, urea resins, epoxy resins, isocyanates, etc.

A few examples now follow in which it is also demonstrated that a monomer precursor is essential from a poly "th ^ rglycol with sufficient -. ohem Molge-wiclrt to manufacture.

Is that: "Follow <.." ot the polyether glycol too low or if only a glycol of iioher ^ iii molecular weight is used, so the stoved films do not have good mechanical properties Properties. In particular, the S

insufficient (Examples V and VI).

V / ird instead of polyatherglycol another Compound of higher ilol weight taken, e.g. dine fatty acid (1.1 = 600) then c> ens insufficiently good mechanical properties are obtained (Example VII).

Examples I and II explain what the influence of the molecular weight of the polyether glycol has on

109839/1366 _SAD

the iik.ch:ni see properties dc ^ ei η cc- burned film is. Examples III and IV demonstrate that the Preliminary product nu ^ h ale- · Χ :: ιΐΰο1: zi.viir Γ.Ι-'tioja-r .n different Functionality produced vä.rdcn can (III) and that the functionality is saturated by installing lin.r Snure ro, -ulu.rai ins st (IV).

The properties of the mentioned in the examples Color film \; urdi η after '.inbrnmieia for 1/2 hour "

The! .Viiibrennlaek VA-.rie in iiiu.r ncr: .ialcn \ / ciee nit jiiiiLüi II «.. laminluirs and Titanweis? in below Relationship;

i; ° p? .lynurisnt 75 GcV / .Ile solid

Mc-laninli-irz 25 Gev;.? Le solid

Titanv. ^ Iss 5? G-c./.Tle

manufactured.

A very good flowability was found in Rllen F ^{1 AIlen, |} a hardened, glossy finish and a very good pre-finish, as well as a good CUiemik-ilitn- ■ bestJ &idigki'it. The an ^ trioL can easily be processed according to the usual methods.

The mechanical properties of the solidified films are checked according to known and established I.Ltheden, In other words, the elasticity na el: Erichseri (in nun), the hard

BATH

10 9 0 :: / ·. 2 6 6

according to K'onig (in seconds) and the impact strength r.zch 3ol (in inch pounds).

■ kl * {jut !, the following can be summed up very well

See combination of properties.

Elasticity 6 mm or more for 120 seconds or more

Impact strength 20 inch pounds or more

Example I. Precursor A molar ratio

1. 1,000 grams of polytetramutylene glycol

(M = 1,000) .1

2. 196 g maleic anhydride 2

3. 500 g Cardura E · 2

1 and 2 in the reactor heat up to 170 ⁰ C; slowly add at 170 ⁰ C. Maintain temperature at 170 ° C until acidity is less than 5.

Preliminary product B molar ratio

1.500 g Cardura E 2

2. 116 g of fumaric acid 1

1 and 2 heat up to 200 ° C. Hold at 200 ⁰ C until acid number less than 5.
K ο ρ ο lyme- ris at
50 g of butanol
50 g xylene
14 g precursor A

109839/1366

9 g pre-product B
57 grams of styrene

Hg 2-2L ethylhexyl acrylate
6 g of methacrylic acid

G

With 3 g of di-tert-butyl hydroxide and 0.8 lauryl mercaptan

copolymerize for about 7 hours at reflux temperature. μ The copolymerization is finished when the pesticide content has become </ o by weight. Properties of the color film after muffling with melamine resin for 1/2 hour at 150 ⁰ O. Elasticity according to Erichsen 6.7 mm hardness according to König 167 sec.

RoI impact strength (reversed) 24 inch, pounds Example II .

Pre-product 0 molar ratio

1,891 g of polypropylene glycol (M = 2,000) 1

2. 87 g maleic anhydride 2

3.222 g Gardura E 2

1,
heat.

1 and 2 in the reactor up to 170 ^° C.

At 170 ⁰ G 3 slowly add; Maintain the temperature at 170 ⁰ C until the acid number has dropped to 5 or lower.

109839/1366

K ^ p olymeri s at .
50 g of butanol

50 g xylene

14 g of butyl acrylate

30 g precursor C

50 grams of styrene

6 g methacrylic acid

G

Mt 3 g of di-tert-butyl peroxide and 0.8 g of iaurylp ·. . ^ reflux for about 7 hours at the boiling point. The copolymerization is complete when the solids content is 50% low. Characteristics of the color film ^ after baking with Molaminharz for 1/2 hour at 15O ⁰ C:

Elasticity according to Erichsen 2> 7 mm Hardness according to k'onig 158 sec.

ReI impact strength (reversed) ^> 80 inch pouuds Example III .

Pre-product D Molvorhaltni o

1. 800 g polypropylene glycol (1/1 = 800) 1

2. 137 g maleic anhydride 1.4

3. 89 g phthalic anhydride ^Λ , 6

4. 500 g Cardura E 2

Heat 1, 2 and 3 in the reactor up to 170 ^° C .; at

109839/1366 _0R1Q1NAL

Add 17O ⁰ C 4 slowly, the temperature being maintained at 170. The end of the reaction is reached when the acid number is lower than 5.

K op oly me ri s at

50 g of butanol

50 g xylene

62 g'styrene * |

19 g of 2-'AthyllK'xyl-icryla. "Fc

13g intermediate product D

6 g methacrylic acid

200 g

Butanol and xylene are heated to reflux temperature (118-122 ° d). The remaining raw materials wcrior ? -., · '. 3 g of di-tert-3-butylperoxy are mixed in and added over a period of 2 hours. The heating mix is then kept at the reflux temperature until a solids content of 50 b has been reached. Properties of the color film after stoving with laminated resin for 1/2 hour at 15C ⁰ H:

Elasticity according to Erichs ^ η 6 mm

Hardness according to King 1 - 5 seconds.

Schlag * lhijkuit r.:>eh Ά <.1 (rev ^ LS <: l) 12 inc'.i, pounds

BAD CRiGSMAL 1 0 9 8:: · / '. 3 6 6

Molar ratio

1 , 9 2 ,8th 1 5

-12-

Boispio: IV

Pre-product E

1.050 g Polytro.mothylenglykol (M = LOOO)

2. 206 Q maleic anhydride ¹

3. 232 J ₃ fumaric acid 4, 1,525 g Cardura E

Heat 1, 2 and 3 in the reactor up to 170 ° C; slowly add at 170 ⁰ G 4. Keep the temperature at 170 ° C until the acid number is less than 5.

Copolyme ri s at

50 g of butanol

50 g xylene 35 g precursor E 49 g styrene

10 g 2- * Ethylhexylacryla ^ 6 g methacrylic acid

200 g

With 3 g of di-tert-butyl peroxide and 0.8 g of Laurylmorcaptrui heat to reflux temperature. About 7 hours on Ruckfliu

keep. The copolymerization is complete when the solid -. ,, w.- ,. ». t- _r ^ ,, ^ ₊ Properties of the color film after stoving with IlclaminJinrz for 1/2 hour at 150 ° E:

ßAD ORiGINAL.

109839/1366

Elasticity according to Erichsen 7 mm

Hardness according to K'onig 154 sec.

ReI impact strength (reversed) 54 inch pound.?

Example V

Pre-product F molar ratio

1. 201 g dipropylene glycol (M = 134) 1

2. 294 g maleic anhydride 2

3. 750 g Cardura E 2

Heat 1 and 2 in the reactor up to 170 ⁰ O. ^Add slowly at 170 ° 0 r. Keep the temperature at 170 G until the acid number has dropped to 5 or lower.

50 g of butanol
50 g xylene

20 g precursor 3 (see Example I) 10g precursor f
50 grams of styrene

14 g of ^2-t Athylhexylacryla
6 β methacrylic acid

G

Maintain the reflux temperature for about 7 hours with 3 g of di-tert-butyl peroxide and Q, Q g of lauryl mercaptave

BAD On: 3! NAL

109839/1366

-H-

(118-122 ⁰ C). The reaction is reversed when the solids content is 50> ί. Properties of the paint film after baking with melamine resin during 1/2 hour at 15O ^C C: elasticity after r.richsen 6.2 mm

Hard after King 136 sec.

ReI impact strength (reversed) 2 inches, pounds

Example VI Pre-product G-haul ratio

1. 118 g of Huxanediol-1,6

2. 115 grams of maleic anhydride

3. 123 & phthalic anhydride

4. 500 g of Cardura E

Heat 1, 2 and 3 in the reactor up to 170 ° C. Add slowly at 170 ° C 4; hold the temperature at 170 ^° C. until the acid number is lower than 5.

1 , 17th 1 , 33 0 2

50 g butane oil 50 g xylene
30 g precursor G 50 g styrene G g methacrylic acid-8 g 2-hydroxy-propylmethe.crylat 6 g 2-ethylhexyl acrylate

200 g

109839/1366 _BAD original

3 3 di-tert-butyl p ^ roxyd and 1 g Laurylmorc & ptan to reflux Wapuratui (118-122 ⁰ J) heat. Hold at reflux for about 7 hours, the copolymerization is complete when the solids content is 50 ". The appearance of the color film after stoving with laminate resin for 1/2 hour at 15 ° C:

Elasticity according to Erichsen 4.6 mm.

Hard for King. 175 sec -

ReI impact strength (reversed) <^ 2 inch pounds

Example yil

Pre- product enveloping ratio

1. 600 g of dimeric fatty acid 1

2. 500 g Oardura E 2 3. 196 g maleic anhydride 2

4. 500 g 3ardura E 2

Heat 1 and 2 in the reactor up to 170 ° C. When an acid number of 5 or lower has been reached, cool down to 120 ° 3. At 120 ⁰ C! is ESpecify 3 au _third Then heat to 170 ° 0. . ™

At 170 ° C., 4 is slowly added, the temperature is kept at 170-175 ° C. The reaction tuond ^ t if the acid number ^ is reached.

1098 39/1366

K ο ρ ο 1 y πι ο risat
50 g xylene
50 g. Butane oil
26 g of preliminary product H
56 grams of styrene

12 grams of 2-ethylhexyl acrylate
6 g of 2, 'etha cry! Acid

200 g

The '.lischung is charged with 3 g of di-tort.-Butylpcroxyd and 0.8 g of lauryl / ^ rcaptan to boiling temperature (118-122 ⁰ C.). Hsch ctv / a. The reaction is complete for 7 hours at reflux. The 7eststoffgoüalt .tiuss 50> o botragua. Properties of the Parbfilns after baking with Melaminzhars for 1/2 hour at 150 ⁰ C;

Erichsen elasticity 6.8 mm

Hardness smell king 170 sec.

RuI impact strength (reversed) ^ 2 inch pounds

BAD ORIGINAL 109839/1366

Claims (5)

-17-CLAIMS. 1. Process for the production of an improved resin binder for muff oil varnish, characterized in that a polyatherglycol of the general formula Hö (Rw) H, in which R represents an alkyl radical with at least 3 carbon atoms and η> with the double: -] ; . η Ilen ge a mono-olefinically unsaturated _Λ dicarboxylic acid or the anhydride ^ ¹ thereof esterified, the dicaibonic acid obtained esterified with the vtoppelr.cl -.- ren amount of a glycidyl _{ester of an α} , _α -dialkyl-substituted alkanecarboxylic acid of the general formula R ₁ 0
R ₂ -C- COOCH ₂ - CH CH ₂ , in which R ₁ , H ₂ and R ₃ saturated alkyl radicals dare tv, Ilen and dc-η ex hold unsaturated ones Diesters with monoclonal unsaturation polymorisbarenori connection kcpolyiueris Lert, 2. The method mch claim Ί, dad-.rch characterized in that the 'χοηο-olefinic' .ingebatti used for esterification Dicarboxylic acid or, whose anhydride is partially by -ein saturated dicarboxylic acid or whose anhydride has been replaced. 3. The method according to Anapr'Vi'ii-n 1-2, characterized in that that a poly "th .rglykol d, r n.llg .-. n.; inen Porae-1 HG (R-O) H, in ckr R represents the group - -0, H- and η ~ 1Ο-2Ο, angov / LiKlot becomes. 4. V ^ ri \ .: hr, n η: <-h dt; η. Anr -.- Λ> uvl ^ r, 1-3, thereby äckunnzcichriut, d'css as glycidyl ^ ct τ -, in-, ί _α , α -Dialkvl-suDGtituic rton Alkanearbons'lure Jardur ^; : -E ar.g-. vvnd .t \ / ird. 5. Vüri '^ hrun after the Anrjprücu ... ·. 1-4 ·, thereby fjcL that ί; .ε hur ^ est ^ llt ^ KopolynxriGat 1C-30 &'^;.; O des x iinyj8i2.ttigt <_- n Di ^ st ^ -rs contains. ; . G-cgens "c? Nd'-, v..rsch; n with> .invrri Ut or zug (, rrial t '. by Ein.cronn -.-- n ^ inor layer, applied with lint-r a according to dun claims 1-5 hi.-r ^ cGt ^ -lltcs resin air; Biii-pi containingon U ^ o 109839/1366