DE2214331A1 - NEW ADHESIVES THROUGH TREATMENT OF THE ETHYLENE AND MALEIC ACID ANHYDRIDE COPOLYMERS WITH AMINO DERIVATIVES - Google Patents

Description

H.6649 - Case 297
03 / AC / GD

22U331

PATENT

New adhesives by treating ethylene and maleic anhydride copolymers with amino derivatives.

Invention: Genevieve NICOUD, married Le Brasseur Adrien NICGO

Joint stock company with the name of the Finns: ETHYLENE PLASTIQQE

309843 / 1ÖÖ8

22H331

This invention relates to new plastics resulting from the reaction of amino derivatives to the statistical Ethylene and maleic anhydride copolymers result.

The ethylene and maleic anhydride random copolymers are known} these substances are produced by copolymerization of a mixture of ethylene and maleic anhydride won under high pressure.

In this invention, the ethylene and maleic anhydride random copolymers are used by weight $ 0.5 - $ 20 in links from maleic anhydride and with a melting number between approx. 0.1 and 100 is used.

It is well known that the anhydride group easily reacts with ammonia anhydride or with the primary or secondary anhydrous amines to form amides and ammonium and amine salts according to the following general scheme:
0

2NH ^J > RC ⁷ -NIT + RC- 0ΝΙΓ

R-C

Il

It was found that the anhydride groups contained in the ethylene and maleic anhydride random copolymers enter into a reaction according to this scheme with ammonia and the primary and secondary monoamines can be made from new plastics with improved adhesion properties and better mechanical properties develop.

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The new plastics according to the invention are in an anhydrous medium by the reaction of an ethylene and maleic anhydride copolymer with ammonia or a primary or secondary monoamine obtained, the possibly in the form of a substituent a carboxylate group from Ba, Sr, -Zn, but preferably from one Alkali metal, especially Na, K, may contain.

According to this reaction, an amide is formed on the one hand and an amide on the other hand at each anhydride group of the copolymer Ammonium salt or a quaternary ammonium salt. It was found that this ammonium or the quaternary Ammonium is replaced by the action of a hydroxide of Ba, Sr, Zn or an alkali metal, preferably Na or K could be and that even better mechanical and adhesion properties resulted from it.

If the reagent contains a carboxylate group, the amino acid salt or the equivalent become indiscriminately Mixture of amino acid + alkaline base used. There may be an existing opposite to the amino acid Excess alkaline base are added, but this excess is less than the stoichiometric Amount of maleic anhydride contained in the original copolymer .

It is assumed that the substances obtained have a structure that follows a statistical distribution Active ingredients corresponds to:

- CE?

-CH CO

CHl CO

CH CONR ²

CH-

COOH

.CH

- CH - COOH

CONRR ¹ - COOK

IP

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with m η ρ q. Number of units

like ^{n +} -P ^{+ q} _ number of active ingredients maleic anhydride ^m "number of active ingredients C ₅ H ₄

in the ethylene and maleic anhydride copolymer.

Non-limiting examples of the primary or secondary amines that can be used are: Diethylamine, diethylamine, the Na or K-Ba-Sr-Zn salts of the glycocolla of glutamic acid, of aminobutyric acid and of amino-11-undecylic acid.

The condensation of ammonia and the amines with the copolymer was achieved using two methods:

A) - By simple contact between the ammonia or the amine in the form of gases or pure vapors or in a mixture with a dry carrier gas (air-nitrogen) and the copolymer in the form of powder or granules (size approx mm at the edge) at a temperature below the melting point of the polymer. The reaction is controlled by the rate of diffusion of the ammonia or the amines in the copolymer. The light amines with a boiling point below 120 ° - (NH, (CEr) NH, (C ² H ⁵ ) ² NH, for example) are therefore preferred.

B) - By kneading calculated amounts of the copolymer - in a plastic mixer, possibly in a nitrogen environment and preferably at temperatures between 120 and 180 with: a primary or secondary amine, a Na-K-Ba-Sr or a Zn salt of an amino acid, or mil; an equivalent Mixture of the acid and one of the metals called hydroxide.

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In addition, an additional quantity of the ketallic hydroxide can be added to these reagents. Furthermore, the substances prepared according to process A) are mixed with a hydroxide of one of the metals mentioned.

A maximum of the primary or. Secondary amines or the salts of amino acids or their equivalent mixture in the Ratio of 1 mole of amine to 1 maleic anhydride active ingredient in the Allow the copolymer and the bases to react in a ratio of 1 base equivalent to 1 maleic anhydride active ingredient in the copolymer.

The ratio of reagents in each pail is effective to choose that the polymer obtained remains thermoplastic, that is, its degree is preferably more than 0.1 or equal to 0.1. The grade is determined according to the ASTM D 1238 standard C 2T described conditions at 190 and one load determined from 2.160 kg. It is obvious that the maximum proportions of usable reagents differ from the original Degree of ethylene and maleic anhydride copolymer and its maleic anhydride content depend.

The substances prepared according to the invention have very interesting properties Properties -that in particular, they adhere strongly to metals and to glass.

In general it could be stated that:

the inventive conversion of the anhydride group of the ethylene-maleic anhydride copolymer with the aid of amines improves the adhesive and mechanical properties of the starting material;

- These properties are increased by treating the product obtained with an alkaline base, the

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Incidentally, the aforementioned treatment improves the adhesion of the product on aluminum more than on copper;

the adhesiveness of these products according to the invention is extremely good on glass;

- the adhesion of the copolymers with treatment the products obtained from the salts of amino acids is very large.

The following non-limiting examples serve to illustrate the invention; in these examples three ethylene and maleic anhydride copolymers as starting products A, B and C used, their composition and Properties are given in Table I below.

Enamel
number TABLE I. fracture
load
(kg / cm2) Young
module
(kg / cm.2) 4.8
41.5
28 100
90
80 1550
1500
2080 Copolymers - 12 ⁰ Jo active ingredients
from maleic acid
anhydride
(Mol / l00g) A.
B.
G 0.036
0.076
0.052 Examples 1

The copolymers were with ammonia or amines in anhydrous Treated medium, either by simple contact in the form of gases (I) or by kneading (II). The implementation conditions (temperature and duration of the reaction) are in the Table II below. The properties of the products obtained are given in Table III below listed.

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■ ν

TABLE II

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Example copolymers

Reagent operating conditions

Type Proportions Process Temp. (C) Duration of the (x) ren reaction

12th
12a

12b

A B A B C A A

A A

A A

HH

Excess excess excess (CH ₃ ) ₂ NH excess (C ₂ H ₅ ) ₂ NH excess

14th

NH ₃

(CH ₃ ) ₂ NH

(CH ₃ ) ₂ NH

Sodium glycocollate

Il

Potassium-

Gl yk ok oll at

Sodium Glut amat

Potassium-

Glycocollate

Potassium aminobutyrate

35 20

35 35

35

NH-

Excess

(CHJ ₂ NH excess

I. 20th 2 hours I. 20th 12 hours I. 20th 2 hours I. 20th . 12 hours I. 20th 12 hours I. 60 4 hours II 150 20 min. II 150 20 min. II 150 20 min. II 150 20 min. II 120 20 min. II 120 20 min. .j-XX 20th 10 hours -J.XX 20th 10 hours

Note ; (x) The proportions of the reagents mentioned in the table are given in moles of reagent per 100 moles of maleic anhydride active ingredients in the copolymer.

xx: The 0.8 mm copolymer powder was mixed with gaseous NH-, od.

Treated excess dimethylamine, then degassed and then kneaded at 120 °.

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TABKLLK III

Examples Melting Index Reaction Breaking Load Young

number (x) kg / cm2 module

kg / cm2

1 4.45 50 /

2 29.5

3 4.8 78 /

4 3.5 74 /

5 29 -

6 4.8 58 /

7 1.4 50 /

8 0.8 64 /

9 2.55 56 /

10 1.2 34 /

11 0.45 69 /

12 0.17
12a 0.4
12b 1.6

(x) Note : The number of reactions reported in this table, determined by the infrared method, is expressed in moles per 100 moles of maleic anhydride actives in the original copolymer.

Examples 13-16

The products prepared in a certain number of the preceding examples were treated with an alkaline base, especially with potassium carbonate; The treatment was carried out in the kneading machine at 120 ⁰ C for 10 min in Example 13, and at 12O ⁰ C for 20 min in Examples 14, 15, 16, 16a-bc and d..; Examples 13-16 used an excess of 20% potassium carbonate relative to the stoichiometry of the reaction; in examples I6a-bc- and d, the molar

309843/1006 " ⁸

90 1,500 125 2,450 129 1,550 110 1.913 150 1,800 135 2,250 150 2,350 147 1,940 105 2,150 140 1,900 155 1,550 123 - 126

22H331

ratios to the!, IaI an acid anhydride given in Table IYa,

The results obtained are given in Tables IV and IVa.

The infrared spectrum of the product obtained according to the conditions of Example 13 confirms the presence of amide
and carboxylate groups, .vie already in Examples 1-6
specified.

Ex. Copolymer
prepares after
example TABLE IV Kaiium-
carbonate Breaking load
kg / cm2 a Degree fracture
load Young
module
kg / cm2 3 30 # 140 0.11 127 2,350 16a 2 Degree 131 0.05 158 1,863 Examples 16b 4th 3.5 Glycocolla 5OfO
30% 130 0.18 150 - 13th 16c 5 2.2 115 0.24 145 - 14th I6d 10.6 $ 30 15th Copolymers
prepares
after
example 5 16 12a TABLE IV - Fracture A. strain A. Reagents 269 12b Amino
acid 292 _ 360 Amino
undecyl
5Of ₀ 284

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Examples 17-22

Examples 17-22 show excellent adhesive properties th of the products according to the invention on metallic Carrier material and on glass.

The tests were carried out as follows: ^a ) Test on a metallic substrate .

The metal is in the form of a 0.08mm or 0.040mm thick film.

The metal is cut into small strips (25 χ 170 mm), which are degreased by immersion in trichloro-III-ethane. The strips are dried in a dust-free environment and stored in the dryer.

The coating is carried out by melting a certain Ilen ge of the polymer in a laboratory press between a Aluminum plates of the size 2 25 x 105 mm and a small strip as mentioned above. Melting temperature and duration are determined with an accuracy of - 1 C and - 1 sec., depending on the experiment. The strenght of the polymer film must be between 100 and 900, µ, preferably are around 200 / u. Under these conditions the Thickness of the film does not affect the adhesive force. This is determined with a tractor (Lhomargy DM 03) Detach the film from the metal at an angle of 180 to the polymer that covers the aluminum plate. The train speed is 100 mm / min. The peeling force is registered according to the peeled length.

A determination is made of the mean force, either directly, if the fluctuations are slight, or statistically, if the adhesion is very irregular (Henry diagram). The adhesive force of a metal film on a given

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ff

Polymer - under certain melting conditions (temperature and duration) - is the statistical mean of the adhesive force of at least 6 samples. The results are expressed in 1O- ⁵ dynes / 25 mm width, the test samples.

b) Experiment on a glass substrate :

If the substrate is a glass plate, then through Melting in the press produces a sandwich layer, which is composed as follows:

1. an aluminum pilm of 80 microns

2. Polymer powder of such a nature that a film of 100-200 microns is recovered.

3. Glass plate 25 x 105 x 4 mm.

The adhesion is determined by peeling off 1 + 2 versus 3.

The operating conditions and the results obtained are listed in Table VI below. In the following Table 5 shows the results obtained using the untreated copolymers A, B, C.

c) Test on a substrate made of polyvinylidene dichloride (PVDCJ "AFCOLAC ¹¹ Gl52"

A film is produced from the copolymer according to the invention; this is painted with a brush with aqueous PVDC emulsion; the emulsion is allowed to dry and then melts under heat in the press.

d) Experiment on other polymer substrates

This attempt is the attempt on metal substrates similar.

e) Trial with epoxy resins, ARALDITE-CIBA "AW 106" (hardener HV 95JÜT

Two films of copolymers according to the invention are bonded with an epoxy resin layer and the whole is heated under pressure.

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TABLE V

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Copolymer

Substrate

Implementation conditions

Adhesiveness

Temp, in ⁰ C duration (min.) Force 1O ³ Dyn / 25

mm

A.
A.
A.
A.

Aluminum 140

Alu 1-90 Alu '190

Copper 140

Copper 140

Copper 190

Copper 190

Aluminum 140

Alu. 190

Copper 190

ordinary

Glass 190

Pyrex glass 190

Aluminum 140

Alu 190

Copper 140

Copper 190

w. Glass 190

Pyresc glass I90

Steel "200

Pyrex glass

PVDC, _s 200

Polyamides (x) 140

Epoxy resins 100

10 10 30

10 30 10 30

10 30

10

10 10

10

30th

10

30th

10 10

2 10

30th

780

650 710

350 530 510

580

860 1,370

1,120

I.3OO 1,560

660 590

880 1,060

2.I5O 940

2050

- 7050 *> 10,000

(x) Type 6-10, SS, 6, 11 and 12 polyamides

09843M006

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COPY

Used
Product, loading - ia. - VI duration 22U331 - rides after
3example TABEL 10 3 30th Ex. 3 Substrate 10 Adhesion
ability ■) 3 Implementation
conditions 30th (Fin) ^{ΚΓ3ίΐ 10}
v -.an; Dyu / 25 mm 17a 3 Alu Temp. ⁰ C 3 1,400 17b 12a Alu 140 . 3 1,520 17c Il Alu 1.40 3 1,350. 17a Il Alu 19c 3 1,420 17e Il stole 190 .2 3,200 17f It Pyreχ glass 200 3 3,500 17g 12b Cellulose-
■ film 200 • ³ 8,600 Cx) ' 17h Il Polyamides 200 3 7ΟΟΟ-9ΟΟΟ 17i Il PV DC 180 3 2200 - 2750 (x 173 ti stole 160 3 3,400 17k 16a Cellulose-
Movie 200 3. > 10,000 171 16b Polyamides 200 3 7000-9000 17m It Sxpoxy 200 • 3 > 10,000 17n Il Pyrex glass 100 3 6,800 17o Il Alu 200 3 2,700 17p. It stole 200 3 6,200 17q Il copper 200 3 I.5OO 17r It Pyrex glass 200 30th 6,850 17s Il cellulose
Movie 200 3 10,500 17t 16c Polyamides 200 3 - 7000-8800 17u Il PVDC 180 ■ 3 1000 - 3000 (2 17v 16a Epoxy 120 6th ^ 10,000 17w 12a. i6e steel 100 10 8,100 17x 7th cellulose
Movie 200 / 30th MO. 000 ' 17y 7th stole 200 7,400 17z dry
wood 200 2000 - 3500 (x) 18a. Alu 160 1,530 18b Alu 140 '1,600 190

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TABLE VI (continued)

- Substrate Perform monetary Duration (outward) Adhesion Doi <-. τ- Used be dingunge η 10 • / errnögen ^
Force 10 ³
Dyn / 25 mm Each X .- 'p. Product, be Alu Temp. ⁰ C 30th 1,450 rides after
example AIu 140 10 1,200 19a 2 copper 190 30th 1,650 19ο 2 copper 190 10 I.9OO 19c 2 Alu 190 30th 1,460 19 & 2 Alu 140 30th 1.6Ö0 20a 14th Alu 190 10 2,150 20b 14th Ku TDf er 140 10 1,700 21a 4th w. Glass 190 10 approx. 3,000 21b 4th Pyrex glass 190 10 5,850 21c 4th Alu 190 10 2,200 21d 4th copper 140 10 1,900 22a 15th ge.7. Glass 190 10 8,000 22b 15th Pyrex Gias 190 5,500 22c 15th 190 22d 15th

(x) Divergent results, adhesive force fluctuates greatly in the course of the test.

Example 23

A terpolymer with $ 12 maleic anhydride and $ 9.5 butyl maleate with the grade value 600 - was in a kneading machine at 140 - 160 ° brought together with laurylamine in a ratio of 10 amine per 100 g of copolymer. The product obtained in this way has a great adhesive force when in contact at 100-150 ° with surfaces made of paper, cardboard and leather is melted and cooled at ambient temperature.

9843/1006

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1S

Example 24

The reaction rate between the copolymer A and the ammonia gas or dimethylamine vmrde with copolymer films examined at 20. It was found that the required for an accelerated reaction (at least $ 30 solid nitrogen in the Atom per LIaIic anhydride group) required time per varies according to the strength according to the table.

Strength NH. HN (OlL.) ₂

mm ^J - *

0.2 1 hour 20 min 35 liin.

1 33 hours 15 hours

2 130 hours 60 hours

The reaction rate was found to be

greater when the temperature was increased to 60.

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Claims (7)

EXPECTATIONS 1. Process for the production of new adhesives, characterized in that that an ethylene and maleic anhydride random copolymer that is $ 0.5-20 by weight illifidern from the maleic anhydride contains and a ochmelt number of approx. 0.1 - 100, is treated with a chemical product made of ammonia and the substances with a primary or secondary amine group wherein said chemical product in the ratio of at most 1 mole of said product per in the copolymer existing anhydride active ingredient is used. 2. The method according to claim 1, characterized in that the primary or secondary amine is an amino acid. 3. The method according to claim 1, characterized in that the primary or secondary amine is an alkaline or alkaline earth Salt or a zinc salt of an amino acid. 4. The method according to claim 2, characterized in that the product is treated with an alkaline base. 5. The method according to claim 1, characterized in that the chemical product is a primary or secondary amine and that the product is treated with an alkaline base. 6. Method of making adhesive scMahtejod. -Coatings, characterized in that at least one layer of a modified copolymer which is obtained according to one of claims 1-5 is applied to a substrate selected from metals and glass. 7. As new products, the modified and according to a of claims 1-5 obtained copolymers. 30984 3/1008