DE2407905A1 - STYRENE-ACRYLONITRILE-MALEIC ACID-COPOLYMERS AND THEIR USE AS GLUE COMPOUNDS - Google Patents

Description

2407S05

PATENT LAWYERS

DR. I. MAAS
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Case 24,873

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American Cyanamid Company, Wayne, New Jersey / USA

Styrene-acrylonitrile-maleic acid copolymers and their use as glue masses

The invention relates to synthetic sizing agents for paper, a process for the production of paper sized therewith Paper and the resulting paper. The term "paper" as used in the present application includes paper, Paper cardboard, hardboard and glued cardboard or cardboard lids.

It is known that polymers contain styrene and ammonium maleamate bonds that correspond to the following formulas

-CH ₉ -CH- -CH ₉ -CH-

^c · and "ι ^d t

'Ties

NH ₂ OH.NH, (D (ID

Have sizing properties, and that paper surfaces which are sized with these polymers are resistant to penetration resistant to water, oil and paint or ink (see PoHart et al, US Pat. No. 3,368,987). In this patent specification

409838/0948

described that polymers containing other water-soluble maleic acid amide salt bonds or aminomaleic acid salt bonds, for example lithium, sodium, potassium, rubidium and calcium jaleamate bonds, also result in good gluing and that these glues together with starch can be used.

Methods suitable for the preparation of polymers of the above type are described in the above patent and also described in U.S. Patent 3,297,620 (Anderson et al).

According to the invention, the adhesive properties of sftyrene-maleic acid amide salt copolymers improved and, in a preferred embodiment, very much improved if they Contain acrylonitrile bonds, especially when they are used on paper as surface glue together with the usual Starch used in papermaking. In the preferred case, polymers result in a substantial proportion of Acrylonitrile bonds and accordingly contain a small proportion of maleic acid am.1 salt bonds, a better one Sizing as they give styrene maleamate salt polymers that do not contain acrylonitrile bonds.

It was believed until the present invention that acrylonitrile bonds Vinyl polymer sizing does not impart superior sizing properties. The reason why the acrylonitrile bonds are effective in the present invention is unknown and applicants do not intend to point to any of them Theory will be limited.

The polymers of the invention allow a superior Sizing after drying them on the paper at an elevated temperature. They result in a glue when they can be used alone as well as when used together with starch.

409838 / Q94B

In the polymers of the present invention are those mentioned above Bonds (styrene, maleic acid amide salt and acrylonitrile bonds) present in average molar ratios from about 1: 0.2 to 1: 0.05 to 0.8. The polymers possess generally the best sizing properties if the proportion of maleamate salt bonds is higher than the minimum and when the proportion of acrylonitrile bonds is high. So are polymers that have these bonds in the range of 1: 0.5 to 0.8: 0.1 to 0.8 are preferred. The polymeric macromolecules vary in their composition in each approach, and the ratios given above give the best average compositions «

The maleamate bonds do not have to be substituted. That is, they can be present as they are in Formula II above are shown.

The above-mentioned metal ions can be used as the salt-forming component use. Laboratory studies have shown, however, that ammonium maleamate bonds (formula II above) give a very satisfactory sizing. Because these bonds are easily formed by the action of ammonia Maleic anhydride bonds are obtained, they are preferred.

If desired, the maleate bonds can be in substituted form. The polymer can thus have dimethylammonium-Ν, Ν-dimethylmaleamate bonds the formula

-CH ₀ -CH

ch;

(III), and

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Methylbutylammonium-NTbutyl-N-meiiiyliaaleamate bonds of the formula

-CH ₀ -CH-

_υ ■ ■ ^V O / CH-R OH. NH _x

CH CH ^C Ü ^H 9 (IV)

contain.

The amide nitrogen atoms do not have to be oil-substituted. the Maleamate bonds can be octylammonium-octylmaleamate bonds the formula

-CH ₀ -CH-

8 ^H 17

NH OH.NH ₀ C

^C 8 ^H 17 (V)

and morpholinium-N ^ -äthylenoxyäthylenmaleamatbindungen der formula

-CH ₀ -CH ₀ -

? S · ο

, N _x OH. I CH ₀ I ²

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It is unnecessary that the substituents attached to the amide groups are bound, correspond to the amines that are present as salt-forming parts of the molecule. The bonds can be methylamine-N-phenylmaleamate bonds the .formula

-CH ₀ -CH-

'X) ¹ O JJH OH.NH ₂ CH ₃ ·

^C 6 ^H 5

(VII)

In the preparation of the polymers according to the invention, it is expedient to use a preformed styrene-maleic anhydride-acrylonitrile terpolymer to start. This polymer can be in organic solution with ammonia or with any desired primary or secondary amine (or a mixture of amines) can be converted to the desired To produce maleamic acid bonds. The maleic acid amide bonds can then be converted into the salt, by adding the appropriate amount of ammonia or an amine, or an aqueous solution of an alkali metal hydroxide can be used add.

The polymer tolerates inert bonds in small amounts, for example in amounts less than 20 mol- #. Examples of bonds of this type are vinyl acetate, methyl acrylate, Acrylic acid, butyl acrylate and acrylamide bonds. These bonds act as "spacers" or as diluents and they do not change the essential character of the polymers.

The molecular weight of the polymers does not appear to be critical and polymers range from 5,000 to 50,000

409838/0948

essentially the same efficiencies. As proof of this it can be argued that polymers below and above this range are also satisfactory.

Suitable amines for the purpose include methylamine, dimethylamine, butylamine, butylmethylamine, octylamine, aniline, oc-naphthylamine, Benzylamine, isobutylamine, cyclohexylamine, and mixtures thereof, in addition to ammonia.

The maleic acid at the 1st bond is hydrophilic and soluble in water in ammonium or alkali metal state. When the 'maleic acid amide bond is in the N-substituted state, the total number of carbon atoms in the substituent should not be so be large that the polymer as a whole becomes insoluble in water. In practice this means that the total number of Carbon atoms in the substituent should be less than about 10. The ammonium (or sodium, etc.) - N-decylmaleamate is thus the most hydrophobic maleamate bond that the polymer tolerates.

The polymer provides effective sizing when applied to paper as a surface size. It is effective when it is present in the paper in amounts as little as 0.01 # based on the weight of the paper, but amounts greater than 3% give little additional benefit that these limits are technical represent a meaningful area. The greatest amount of sizing per increment of polymer present in the paper is between 0.1 and Λ% ₉ and this is therefore the most preferred range.

The polymer is most advantageously used in conjunction with starch. You get particularly favorable results if that Weight of strength in the range of 1 to 200 times, based on based on the weight of the polymer. However, good sizing is also obtained if the weight of the starch is between 2 and 20 times the weight of the polymer, which is therefore a preferred

409838/0948

area is. One can use any of the usual water soluble ones Use starches to make paper, for example cooked grain or corn starch, oxidized starch and chlorinated starch.

The polymer is best used as an aqueous dispersion containing from about 0.01 to about 3 weight percent polymer, and preferably from Contains 0.1 to 1% by weight of polymer. If so desired The dispersion can contain 1 to 10% by weight of starch for papermaking contain.

The paper according to the invention is produced by 'one that Paper glued or glued to the surface with an aqueous dispersion of the polymer with or without starch. The dispersion is done with a size press or with a smoothing press or a calender or a calender pyramid (calender stack) applied in a sufficient amount so that the desired gluing is achieved. Can be a suitable amount in any case can easily be determined by a trial.

The following examples illustrate the invention without restricting it.

example 1

The following describes the production of a glue mass according to the invention described

59.5 g of styrene, 47 g of maleic anhydride and 4.9 g of acrylonitrile (1: 7/8: 1/6 molar ratio) are added to 746 g of toluene while stirring under a nitrogen atmosphere, and then 0.13 g of azobisisobutyronitrile is added as Add catalyst. The mixture is held at 80 to 100 ° C. for 1.5 hours. A further 0.08 g of catalyst are then added and the mixture is kept at 95 to 100 ^° C. for a further 1.5 hours. A polymer slurry forms.

U 0 9 8 ?. 3/0 9 4 H.

The slurry is cooled to 80-85 ° C and 69.4 g 28% aqueous ammonium hydroxide (1.14 mol) in 1CX) ecm water are admitted.

The mixture is stirred rapidly for 30 minutes, after which the toluene is removed by steam distillation. The residue is an 18% strength by weight solution of a vinyl polymer which is essentially Styrene bonds, water soluble ammonium maleamate bonds and acrylonitrile bonds in the ratio given above.

Example 2

The procedure of Example 1 is repeated with the exception that the amount of ammonia is reduced to 33.7 g and that after the reaction of the ammonium hydroxide, 23 g of sodium hydroxide (made up to 90 ecm with water) slowly added, until the pH of the solution is 8.5.

The product is a styrene-sodium maleamate-acrylonitrile polymer.

Example 5

The procedure of Example 1 is repeated except that the ammonium hydroxide is omitted and that instead 104 g of a 50% strength aqueous solution of dimethylamine are added.

The product is a polymer containing styrene, dimethyl-N, N-dimethylmaleamate and contains acrylonitrile bonds in the aforementioned ratio.

Example 4

The procedure of Example 1 is repeated except that the ammonium hydroxide is omitted and that 147 grams of octylamine be added together with 250 ecm of water.

8-38 / 0948

The resulting polymer contains styrene, octylammonium N-octyl maleamate and acrylonitrile bonds in the aforementioned ratio.

Example 5

The procedure of Example 1 is repeated with the exception that the ammonium hydroxide is replaced by 99.5 g of morpholine in 250 ecm Water is replaced. The resulting polymer consists of styrene, morpholine-N ^ -äthylenoxyäthylenmaleamat- and acrylonitrile bonds in the aforementioned range.

Example 6

The comparable sizing properties of the polymers according to the invention are explained below, the proportion on acrylonitrile bonds is varied.

A number of polymers are produced. The first polymer is made by adding 10 moles of styrene with 10 moles of maleic anhydride polymerized and the maleic anhydride bonds converted into ammonium maleamate bonds, whereby the procedures described in Example 1 were used. The rest of the polymers are made in the same way, except that instead of maleic anhydride mixtures of maleic anhydride and acrylonitrile, a total of 10 moles, in the in the following table I can be used. In either case, the maleic anhydride bonds converted to ammonium maleamate bonds according to the procedure of Example 1.

A set of glue solutions is made by taking aliquots of a 5 wt. & Lb. laboratory solution of starch for papermaking takes and to this adds sufficient amounts of the polymers produced in this way, in each case 0.05% by weight of polymer, based on the weight of the aliquot.

4098 3 8 / 094K

A second set of glue solutions is prepared in the same way, except that each solution contains 0.1 % polymer based on the weight of the solution.

An aliquot of the starch solution is retained as a reference.

The sizing properties of the resulting polymers are determined in a standard laboratory manner using in each case a sheet of unsized, 50:50 bleached Kraft hardwood: pine paper sheet approximately 22.7 kg (50 lbs.) G by weight (25 "x 40" / 500) passes through one of the glue solutions, excess solution from the sheet is pressed through the sheet between blotting sheets, the sheet is dried for 1 minute on a laboratory drum dryer with a drum temperature of 115.6 ⁰ C (240 ⁰ F), an ink stain on the underside of the horizontally held sheet and note the number of seconds required until the upper side of the sheet shows a decrease in brightness of 20% above the stain, due to the absorption of the ink or the color. The paper sheets absorb 100% of the glue solution based on their weight. In each case the glue solution contains approximately 5% starch. The sheets in the first set contain approximately 0.05% polymer. The sheets in the second set contain approximately 0.1% by weight. % Polymer, and the following results are obtained.

Tabel

Ver Polymer Composition - Mol 10
10
10
10
10 2
4th
6th
8th Ammonium-
maleamat 0 Gluing, sec. 0.1% ² search
No. Styrene acrylic
nitrile ¹ contains 5 ^1, 05% [2] Comparison ^{1 2} wt.
pier 10
8th
6th
4th
2 1 [2] 63
225
226
243
493 1
2
4th
5. Weight% starch, but no polymer 2
2
9
44
12th % of the polymer in the paper.
5% by weight starch the pa- , In any case
* contains

It 409838/09 ^ 8

Example 7

The procedure of Example 1 is repeated, with the exception that one dispenses with the addition of ammonium hydroxide and that the polymer dispersion is cooled to room temperature Gaseous ammonia is then slowly passed through the solution, until it shows a weight gain of 20 g (approximately 1 hour). The solution is stirred for 30 minutes, filtered and the solvent is removed. The product is a dry, free flowing powder and possesses the same Sizing properties like the product of Example 1.

Example 8

20 g of the polymeric powder from Example 8 are mixed with 100 g of dry, water-soluble starch for papermaking and a trace of bio-envy mixed together. Half of the mixture is kept for 1 month in a sealed bottle at room temperature stored.

The other half of the mixture is in about 100 ecm of water dissolved and the solution is sealed in an egg for 1 month Bottle stored at room temperature *

By the end of the month, both the dry mix and the solution are essentially unchanged and both have essentially the same sizing properties.

409838/094 8

Claims (3)

^j - 12 - Claims Vinyl polymer containing styrene and maleic acid amide salt bonds, characterized in that it additionally contains acrylonitrile bonds, the relative Molar ratios are 1: 0.2 to 1.0: 0.05: 0.8 of styrene to maleic acid amide salt to acrylonitrile. 2. Method of using gluing paper an aqueous dispersion of a polymer dispersion, characterized in that the polymer of claim 1 used. 3. Paper, sized with a polymer mass, thereby characterized in that the composition of Example 1 is used. 409838/0948