DE2442382C3 - Process for the manufacture of a paper-forming material - Google Patents

Description

CH CH-

I I

C = O C = O

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and or

CH, -

-CI- R ₂

-fCH, -

-CH ₂ -C-

C = O

I. O

A.
CH ₃

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C = O

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From GB-PS 13 23 174, FR-OS 2 60 915, JP-AS 73 13 722 and JP-AS 73 13 723 it is known paper-forming material by extruding an emulsion of a poly-oc-olefin, an organic one Solvent, a dispersion medium, welcnes a nonsolvent for the poly-α-olefin and im is essentially incompatible with the organic solvent, and a surface-active agent! as Create a beam through an opening. In this way manufactured fiber materials can be used alone or together

2s men with cellulose to make papers with excellent mechanical properties, excellent brightness and opacity. The after the However, paper-forming materials produced by known methods form when whipped in water Bubbles through which the whipped fibers rise to the surface of the water. This leads to significant Difficulties in papermaking, especially in beating the fibers, and results in a unevenly textured paper.

The object on which the invention is based then consisted of expansion spinning to get paper-forming material with better properties for papermaking, in which As far as possible, there is no bubble formation and no extraction of surface-active agent by the water, which retains its hydrophilic properties and leads to a uniformly structured paper

The inventive method for production a paper-forming material by extruding an emulsion of a poly-α-olefin, a organic solvents with a boiling point lower than the melting point of the poly-yn-olefin. a dispersion medium which is a nonsolvent for the poly-oc-olefin and essentially incompatible with the organic solvent. and a surfactant as a jet through an opening, is characterized in that one as a surfactant Average 0.5 to 40% by weight, based on the weight of the pole) volefin. of a polymer Structural units of the formulas

(IV) a vinyl monomer grafted polyvinyl alcohol wherein A and B are Li, Na. 1/2 Ca, 1/2 Mg, 1/2 Zn or 1/3 Al, Ri a hydrogen atom or a hydrocarbon radical with 1 to 30 carbon atoms, Ri a hydrogen atom, the group - COORj (R ₁ = hydrocarbon radical with I to 30 carbon atoms), the group - OCOR4 (R4 = hydrocarbon oil with I to 20 carbon atoms), a halogen atom or the group -CH ₂ OH, R ₅ the group -OH CH

CH

ί
C = O

I. ο

CH ₂ C

and or

C = O

I. ο

CH, - C

-Calcium methacrylate copolymers or Olefin sodium or -Calcium acrylate copolymers, (II) ethylene-vinyl acetate copolymers,

Styrene lauryl methacrylate

Sodium methacrylate copolymers, saponified ethylene-vinyl acetate copolymers, Ethylene-allyl alcohol copolymers and Poly (sodium methacrylate).

CH ₁

+ CH, - C -

C = O

I. ο

CHj-C-- R,

•

and or

and or

tCH, - CH

(Uli

(IV) a vinyl monster grafted Po! Yvin.y! A! Koho !, where A and BLi. Na, 1/2 Ca, 1/2 Mg, 1/2 Zn or 1/3 Al mean, Ri means a hydrogen atom or a hydrocarbon radical with! to JO means carbon atoms. R; a hydrogen atom denotes the G-jppe - COORi (Rj = hydrocarbon radical with t to 30 carbon atoms), the group -OCOR ₄ (R4 = * 'hydrocarbon radical with 1 to 20 carbon atoms), a halogen atom or the group —CH2OH. R 1 denotes the group —OH or the group —CHjOH, and the polyolefin in a concentration of 5 to 40% by weight. based on the organic solvent.

The surface-active agents used according to the invention not only have an emulsifying effect, but also also give the paper-forming material hydrophilic and self-binding properties. You can use the Mixture with one another can be used, whereby, by appropriate selection, any desired balance of hydrophilic and lipophilic properties can be obtained can get. The surface-active agents used according to the invention result in better surface strengths of the paper, even if the synthetic paper-forming material contains cellulose fibers is mixed than when using customary cement or surface sizing.

Preferably used surface-active agents with the structural units of the formulas I, II or III are

Styrene-sodium maleate copolymers, Styrene-alkyl methacrylate-calcium or

-Sodium maleate copolymers,

Ethylene sodium, calcium or

-Aluminum maleate copolymers,

Ethylene-olefin-sodium or

-Calcium maleate copolymers,

Ethylene-sodium acrylate copolymers, Olefin sodium or

All of these surfactants have a hydrophilic component such as an alkali salt group, and a lipophilic component such as a polymer chain or Carbon residues of hydrogen.

In the case of using vinyl monomer grafted polyvinyl alcohols (IV) as surface active agents it is appropriate to use one with styrene, vinyl acetate, acrylic acid, methacrylic acid or esters of acrylic acid or Use methacrylic acid grafted polyvinyl alcohol. Water soluble monomers such as acrylamide and Acrylic acid, when grafted onto polyvinyl alcohol, have a lower surface-active effect because Graft copolymers obtained in this way have poorer lipophilic properties. It's functional for the vinyl monomer grafted polyvinyl alcohols completely or partially saponified polyvinyl alcohol with a degree of polymerization of 200 to 4000 use.

The graft polymerization of the vinyl monomers onto the polyvinyl alcohol can be carried out with an aqueous polyvinyl alcohol solution with free radical initiators such as ammonium persulfate, potassium persulfate, cerium ammonium nitrate or organic peroxides.

The vinyl monomer grafted polyvinyl alcohols are firmly fixed to the poly-a-olefin, whereby a Bubble formation does not occur when beating in an aqueous medium and the paper-forming fiber material acquires hydrophilic properties. The vinyl monomer becomes on the polyvinyl alcohol expediently in an amount from 5 to 2000, preferably from 25 to 500 % By weight, based on the polyvinyl alcohol, grafted on. If the grafted amount of the vinyl monomer is too small, the surface active agent possesses (IV) has a less lipophilic character and is therefore easily miscible with water. When the amount of On the other hand, the grafted vinyl monomer is too large, the agent has insufficient surface-active properties. The formation of homopolymers of the vinyl monomer in the graft copolymerization disturbs the Surfactant effect does not.

The amount of the surfactants added in the present invention is preferably about 1 to 30% by weight based on the weight of the polyolefin.

These polymeric surfactants according to the invention can also be used together with conventional ones low molecular weight surfactants can be used. Specific examples of this are anionic surface active agents such as carboxylic acid salts, sulfuric acid esters, sulfonic acid salts and phosphoric acid esters, cationic surface active agents, anionic and cationic surface active agents such as amine acid salts and betaine compounds, as well as nonionic surfactants such as polyethylene glycol compounds and polyhydric alcohols.

It is also possible to use other hydrophilic or water-soluble polymers, pigments, stabilizers, Antistatic reagents, binders, sizing agents or other substances to be added to the poly-a-olefin

The poly-α-olefins used according to the invention are for example polyethylene, polypropylene, poly-I-butene, Poly-4-methyl-1-pentene and copolymers of two or more -olefin monomers.

The organic solvents used are hydrocarbons such as pentane, hexane, heptane and benzene as well chlorinated hydrocarbons, such as methylene chloride and chloroform, can also be considered mixed Solvents can be used.

Water, glycerin, glycol and mixtures thereof can be used as the dispersion medium. in the water is generally used.

Dispersion medium and organic solvent are expediently in a volume ratio approximately ! : 6 to 6: 1 used.

Examples of preferred compositions of poly-α-olefin and surfactants are the following:

Parts

A. Polypropylene 100 Ethylene Vinyl Acetate Copolymer 20 Ethylene Sodium Acrylate Copolymer 3 Sodium Dodecylbenzenesulfonate 3

B. Polypropylene 100 styrene-sodium maleate copolymer S Styrene-Caleium Maleate Copolymer 1

C. Polyethylene 100 styrene-methyl methacrylate-sodium maleate copolymer 10 sodium dodecylbenzenesulfonate 3 calcium stearate 2

D. Polypropylene 80 Polyethylene 20 Polyvinyl alcohol 3 Saponified ethylene-vinyl acetate copolymer 5 styrene-methyl methacrylate-lauryl methacrylate-sodium maleate mixed polymer 3

E. Poi / propyltn 80 polyethylene 20 Chlorinated polypropylene 15 calcium sulfate 20 ethylene-calcium acrylate copolymer 3 Sodium dodecylbenzenesulfonate 2

F. Polypropylene 65 Ethylene Sodium Acrylate Copolymer 15 Styrene-methyl methacrylate-sodium maleate copolymer 3 styrene-methyl methacrylate-calcium iimaleate copolymer 1

G. Polyethylene 100 Calcium Carbonate 20 Saponified ethylene-vinyl acetate copolymer 5 styrene-octene-sodium maleate copolymer 3

H. Polypropylene 100

Styrene-grafted polyvinyl alcohol 10

I. Polypropylene 100

Polyvinyl alcohol 5

Styrene-grafted polyvinyl alcohol 5

The preferred Exirudiertemperatur during expansion spinning is about 100 to 200 ⁰ C. Above 200 ⁰ C, the emulsion will lose its stability often spiders The expansion can be carried out at autogenous pressure or at a pressure higher than the autogenous pressure. The pressure can be generated by gases such as hydrogen, nitrogen, argon, carbon dioxide, methane, ethylene or propylene. Usually the extrusion is done at a pressure of about 5 to

ίο 100 kg / cm ² .

The shape of the extrusion nozzle is important because the polymer is molecularly oriented in the disperse phase Should solidification occur with the removal of organic solvents during extrusion of the poly-ot-olefin. The solvent removal takes place before the orientation of the polymer is reversed, so that the poly-α-olefin its Maintains orientation

The extrusion nozzle can be round or non-round, such as rectangular, in cross section. The preferred nozzle diameter (circle described inside) is 0.2 to 20 mm. With smaller diameters, the nozzle tends to become clogged. With nozzle diameters larger than about 20 mm, it is difficult to obtain adequate molecular orientation of the poly-α-olefin. The ratio of length to diameter of the extrusion nozzle is favorably about 0.1 to 100, preferably about 02 to 10.

The particle size of the emulsion is generally between about 0.1 and 100 μ. The solvent removal the extrusion takes place by evaporation and / or cooling. It is therefore desirable to have the emulsion to be sprayed out at a temperature which is higher than the boiling point of the solvent and / or the dispersion medium In some cases the extruded product has the appearance of a cotton ball, but leaves this aggregation of short fibers can easily be broken down by whipping. The hitting is done in the usual way with Dutch, PFI mills. Beater mills or the like, and then the pulp can be mixed with wood cellulose.

At any stage of the process, a sizing agent for engine sizing can also be added to the stock and aluminum sulfate can be added. The sizing agent for this is usually used in an amount of about 0.5 to 10% by weight, based on the weight of the poly - * - olefin and optionally the wood cellulose used. Examples of such sizing agents are polyvinyl alcohol, carboxymethyl cellulose, methyl cellulose. Strength. Paste, algine. Wax emulsions. Alkyl ketene dimer. Rosin, montan wax, silicones, Asphalt. Bad luck. Sodium silicate. Casein, urea resins. Melamine resin. Polyethyleneimines. synthetic latex emulsions. Polyvinyl acetate emulsions, polyacrylamide

S5 and its mixed polymers

The stock concentration in papermaking is expediently about 0.01 to 10% by weight. After dewatering and drying the sheet of paper *, around 80 t ^; s 120 "C, the paper is advantageously subjected to surface sizing with known surface sizing agents or with the polymeric agents from the structural units of the formulas I to IV. Approximately 0.1 to 5 g of sizing agent per square meter of paper are expediently used.

In addition, it should be noted that the surface-active agents with the structural units of the formulas! to 111 suitably have a molecular weight of about 10,000 to 1,000,000.

Example I.

A mixture of 100 g isotactic polypropylene powder with an η value of 2.3 dl / g, 20 g acrylonitrile-styrene mixed polymer (weight ratio of AN / ST = 24/76), 5 g sodium maleate-styrene-methyl methacrylate mixed polymer (50 / 30/20 in mole ratio), 1.151 methylene chloride and 1.41 water to 140 to 150 ⁰ C during 30 minutes under stirring with 700 U / min, heated in a steel autoclave with an internal volume of 5 1 and emulsified. Subsequently, when the valve has a nozzle with a diameter of. 1.6 mm and a length of 1.0 mm was opened, the fiber material was expelled under autogenous pressure (about 17 kg / cm ² overpressure). 42 g of sprayed material (corresponding to 3 g dry weight) were easily divided up in a mixer together with 750 ml of water over a period of 5 minutes. During the fragmentation

Example 2

A paper-forming material was made from a mixture of 95 g of isotactic polypropylene powder with an η value of 2.3 dl / g, 10 g of acrylonitrile-styrene copolymer (Weight ratio of AN / ST = 24/76), 7 g of styrene-sodium maleate copolymer, 1.15 1 Methylene chloride and 1.4 l of water were obtained by the same method as in Example 1.

After disassembling the paper-forming material in a mixer, a sheet of paper was made into two parts of this material and 8 parts of cellulose paper stock by the same procedure as in Example 1.

This paper sheet had a wax absorption strength of 3 Å and an IGT surface strength from 232 cm / sec.

Example 3

A paper-forming material was made from a mixture of 140 g of isotactic polypropylene powder with an η value of 1.7 dl / g, 2 g of poly vinyl alcohol, 7 g Sodium butyl maleate-styrene-methyl methacrylate copolymer (Molar ratio 50/30/20), 1.15 l of pentane and 1.4 l of water by the same procedure as in Example 1 obtain.

After breaking up the paper-forming material in a mixer, a sheet of paper (only from this material) with a fracture length of 2.5 km.

Example 4

A paper-forming material was made from a mixture of 120 g of isotactic polypropylene powder with an η value of 1.7 dl / g, 3 g of polyvinyl alcohol, 5 ρ

vigorous stirring.

0.6 g (on a dry weight basis) of this fiber material with good dispersing properties were combined with 24 g (on a dry weight basis) of cellulose paper (mixture of NBKP / LBKP = 2/8, freeness 450 ml) to form a moist hand sheet using the Tappi standard method T205o ? 71 deformed. This moist sheet was ^{dried for 2 minutes at 110 °} C. and then pressed with a roller with a pressure of 40 kg / cm ^2.

The obtained paper sheet had a wax absorption strength (Tappi T 459 su-65) of 6 A and an IGT surface strength (Tappi T499su-64) of 185cm / sec.

Comparative example

A paper-forming material was made from a mixture of 100 g of isotactic polypropylene powder with an η value of 2.3 dl / g, 3 g of sodium dodecylbenzenesulfonate, 2 g of calcium dodecylbenzenesulfonate, 1.151 methylene chloride and 1.41 of water by the same procedure as in Example 1 obtain.

When this fiber material was broken down together with water in a mixer, the sludge foamed strong, and the fibers tended to swim. Thus, this material was poor in dispersing properties and resulted in a paper sheet (made from 20% of the fiber material and 80% cellulose paper) with poorer uniformity. This sheet of paper had a wax absorption strength below 2A.

propylene glycol (30) ethylene oxide (10) phosphate, 1.151 Hexane and 1.4 l of water were obtained by the same method as in Example 1.

After dicing the material in a mixer, a paper sheet had (synthetic only from this pulp consisted) a breaking length of 2.3 km, and a paper sheet (which be from two parts of this synthetic paper pulp and 8 parts Cellulosepapicrsioff nand) had a breaking length of 3, b km.

Example 5

A mixture of 100 g polyethylene powder, 30 g calcium carbonate, 3 g sodium maleate-styrene-methyl methacrylate-lauryl methacrylate mixed polymer (Molar ratio 50/30/15/15), 1 g calcium maleate-styrene-me-

ethyl methacrylate-lauryl methacrylate copolymer
(Molar ratio 50/30/15/15), 1.15 g of hexane and 1.4 l of water were emulsified and sprayed out by the same method as in Example 1.

The expelled material was easy to dismantle and well dispersed in water. A sheet of paper from this paper-forming material (only from the synthetic paper stock) had a breaking length of 5 km, and a Sheets of paper (made from 2 parts of the synthetic paper stock and 8 parts of cellulose paper stock) had a Wax absorption strength of 7 A.

Example 6

A solution of 100 g of polyvinyl alcohol (in 1 liter of water and a nitrogen atmosphere) was placed in a 2-1 four-necked flask equipped with a stirrer, a condenser and two dropping funnels. While stirring this solution at 6O ⁰ C 100 g of styrene monomer and a solution of 2.28 g ammonium persulfate in 100 ml of water was added through the funnel over one hour. After the addition of the styrene and ammonium persulfate, the reaction mixture was stirred at 60 ° C. for 4 hours.

Part of the reaction mixture was in a large excess of methanol poured. The coagulated polymer was filtered and then several times with Methanol washed. The styrene conversion was about 100%. and the grafted polystyrene in that polymerized styrene (which was not extracted by boiling benzene) was about 78%.

A mixture of 6 g of styrene-grafted polyvinyl alcohol obtained by the above process (used without isolation from the reaction mixture), 94 g of isotactic polypropylene powder with a?) Value of 2.3 dl / g, 0.5 g of 2.6- di-tert-butyl-4-methylphenol, 1.15 1 of methylene chloride and 1.381 of water was heated with stirring at 700 rev / min, in a steel autoclave with an inner volume of 5 I to 140 ⁰ C and emulsified. Then, when the valve of a nozzle with a diameter of 1.6 mm was opened, the fiber material was expelled under autogenous pressure (about 17 kg / cm ² overpressure). 40 g of sprayed material (corresponding to 3 g dry weight) were divided up together with 750 ml of water in a mixer for 5 minutes. This pulp slurry did not foam while stirring.

0.6 g (based on dry weight) of this fiber material with good dispersing properties were combined with 2.4 g (based on dry weight) cellulose paper (mixture of NBKP / LBKP = 2/8, degree of freeness 450 ml) to form a moist hand sheet after the Tappi Standard method T 205 05-71 deformed. This moist sheet was ^{dried for 2 minutes at 110 °} C. and then pressed with a roller at a pressure of 40 kg / cm ^3.

The paper sheet obtained had a basis weight of 52.5 g / m ² , a brightness of 85.5%, and an opacity

10

of 77.2%, a breaking length of 4.14 kg and an IGT surface strength of 160 cm / sec.

Examples 7-11

Various vinyl monomer-grafted polyvinyl alcohols prepared according to the same procedure as in the example 6 are shown in Table I.

Table I.

sample Grafted mono- mono- Monomer No. Monomer mer / PVA merum- graft Wall- efficiency. lung. % % A. Styrene 2/1 100 35 B. Styrene 1/1 100 45 C. Styrene 1/1 100 90 D. Methyl- 1/1 100 69

Styrene

1/2

100

70

Using these vinyl monomer-grafted polyvinyl alcohols, expansion spinning was carried out, using the same procedure as in Example 6. The properties of the obtained paper-forming fiber materials are listed in Table II.

Table II

Example Spinning Composition Used

No. Grafted Polypropylene Grafted

PVA PVA

Foaming sheets of paper
Fracture length

(km)

IGT surface strength
(cm / sec.)

9 Ai) 90 10 none 3.56 115 8th B ') 85 15th none 3.87 231 9 O) 90 10 none 3.74 150 10 D ") 70 10 none 3.81 142 11th Egg) 90 10 barely 3.90 161

') According to table V.

example

A mixture of 70 g of isotactic polypropylene powder with an η value of 2.3 dl / g. 1 g polyvinyl alcohol, 20 g ethylene-vinyl acetate copolymer, 3 g styrene-methyl methacrylate-lauryl methacrylate-sodium maleate

Mixed polymer (molar ratio 30/15/5/50), styrene

Methyl methacrylate-lauryl methacrylate-calcium maleate- 55 mass sizing ¹ ) mixed polymer (molar ratio 30/15/5/50), 1.15 1 hexane and 1.4 1 water was emulsified and sprayed according to the same method as in Example 1

The sprayed material was divided up together with water in a mixer.

The synthetic pulp obtained was formed into a paper hand sheet and either sizing agent treated for in-situ sizing or not

The surface strengths of paper sheets made from 2 parts synthetic paper stock and 8 parts cellulose paper stock are shown in Table III.

As can be seen from Table III, the surface strength was by using a combination of in-situ sizing and surface sizing with polyvinyl alcohol greatly improved

Table III

Surface wax absorption sizing ² ) strength
(g / m ² )

None

None

Ia ³ )

I-aJ) Polyethyleneimine

Polyethyleneimine

1) The amount of sizing agents based on 3.2% by weight, based on on the synthetic paper stock.

μ Polyvinyl alcohol was used.

³ ) styrene-methyl methacrylate-lauryl methacrylate-sodium maleate mixed polymer (molar ratio 30/15/5/50).

0 2A 0.9 5A 0 4A 1.0 8A 0 2-3A 03 8A

Example 13

A mixture of 62 g polypropylene powder with an η value of 2.3 dl / g, 3 g polyvinyl alcohol, 18 g ethylene-sodium acrylate copolymer, 3 g styrene-methyl methacrylate-sodium maleate copolymer (Molar ratio 30/20/50) and 1 g of S'yrene-methyl methacrylate-calcium maleate mixed polymer, 1.151 hexane and 1.41 water were prepared using the same procedure as in Example 1 emulsified and sprayed out.

The sprayed material was together with

Divided water in a mixer. The obtained pulp was made together with cellulose pulp after adding a sizing agent for mass gluing deformed into a sheet of paper.

The surface strength of paper sheets made from two parts of the synthetic paper stock and 8 parts ίο Cellulosic stock is shown in Table IV.

Table IV Surface sizing Amount, g / m ³ Surface strength IGT upper Cement sizing ¹ ) middle wax surfaces recording strength strength (cm / sec.) no 120 none 15th 4A None PYA no 7 A ι / ";" ".. none 1.0 7A > 390 la *) PVA 1.5 8A l-a *) I-a 0.35 7-8A I-a *) cationic starch 0.48 7A I-a *) Calcium salt of poly 8A Ia ^) acrylic acid 1.3 > 390 PVA 8A I-b ^

') 3.3% sizing agent and 4% aluminum sulphate (% by weight, based on the synthetic paper stock) were used.

² ) The same means as shown in Table III.

³ ) Styrene-methyl methacrylate-sodium maleate mixed polymer (molar ratio 30/20/50).

example

A mixture of 70 g of isotactic polypropylene powder with an η value of 2.3 dl / g, 2 g of polyvinyl alcohol, 3 g sodium dodecylbenzenesulfonate, 2 g calcium dodecylbenzenesulfonate, 1.151 hexane and 1.41 water emulsified and sprayed using the same procedure as in Example 1.

The sprayed material was divided up together with water in a mixer.

The synthetic stock obtained was shaped into a paper sheet after being sized. the Surface strength of paper sheets made from two parts synthetic paper stock and 8 parts cellulose paper stock is shown in Table V.

In this case, the surface strength was not significantly improved by the gluing.

Table V Surface sizing Wax absorption Ingot sizing PVA, g / m ² strength I-a *),% ') none <2A None 0.6 3A None none <2A 3 0.8 4A 3 none <2A 6th U 3A 6th

¹ J 1.7% (based on the synthetic paper stock)

used
² ) The same material as shown in Table III.

Based on the synthetic paper stock.

Claims (1)

Claim: Verlihren for the production of a paper-forming Materials by extruding an emulsion of a poly - * - olefin, an organic solvent with a lower boiling point than the melting point of poly-a-olefin, a dispersion medium, which is a nonsolvent for the poly-olefin and essentially incompatible with the organic solvent, and a surface-active agent as a jet through an opening, characterized in that the surfactant is 0.5 to 40% by weight, based on on the weight of the poly-a-olefin, one Polymers from structural units of the formulas or the group —CHjOH denotes, and the poly-Λ-olefin used in a concentration of 5 to 40% by weight, based on the organic solvent.