DE2309129A1 - METHOD OF GRAFTING ORGANIC POLYMER FROM INORGANIC SUBSTANCES - Google Patents

Description

β 1.1 Q ι. C ίι * η 25, ti-.ein «etc., - iotr. IO

024-20.254Ρ February 23, 1973

LION OIL & FAT COMPANY, LTD. Tokyo (Japan)

Process for grafting organic polymers from inorganic substances

The invention relates to a method for producing composite materials from an inorganic Substance and an organic polymer, which are useful as molding compounds or plastic fillers. In particular the invention relates to a method for the production of inorganic substances with grafted organic polymers.

For grafting organic polymers such as polyvinyl chloride, polymethyl acrylate, polymethyl methacrylate and Polystyrene on different metals or inorganic

NöGs

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Various methods have been proposed for substances such as Fe, Ni, ZnO, TiO ₂ , BaSO ^, silica gel, quartz and carbon black. Representative of these are a mechanical activation grafting method and a radiation polymerization method. An example of mechanical activation is the chemical grafting of organic polymers, described by VAKargin and others, onto freshly formed surfaces of metals and alkali metal salts by grinding or rolling (see Vysckomol, Soedin. J_ (1959) pages 330-331 and 1713-1720 ). An example of the radiation polymerization process is that of Tsetlin et al. In Akad. Nauk SSR, Otd. Khim.Nauk, Moscow 1960 , p.497 described grafting of polymethyl methacrylate, polyacrylonitrile and polyvinyl chloride onto carbon black, powdered silica gel and MgO at 40-50 ° C under β-radiation.

The initiation of the polymerization of organic monomers through the formation of new crystal faces on inorganic ones Substances by mechanical means such as pulverization with grafting of the organic polymer onto the however, the inorganic substance has the disadvantage that it is difficult to obtain sufficient amounts of the polymer thereafter to apply to the inorganic substance, since only a limited number of active sites on the crystal faces is formed and the method is otherwise only applicable to crystalline inorganic substances. On the other hand, radiation polymerization is not particularly suitable for commercial production, as it requires special equipment and the observance of many safety precautions. Thus all are known Process for grafting organic polymers

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on inorganic substances associated with various disadvantages for commercial manufacture and therefore difficult to implement in practice.

The aim of the invention is therefore a method for grafting organic polymers onto inorganic substances by chemical action or treatment, without the need to carry out more complicated procedures in particular mechanical treatments.

Other objects, features and advantages of the invention will appear more clearly from the description below.

The state of organic polymers attached to inorganic substances is here called "grafted on" denotes, which is supposed to mean that the organic polymers are so firmly bound to the inorganic substances are that they cannot be easily removed by extraction with a solvent, like it would be the trap in the case of mere adsorption or adhesion.

The term "radical polymerizable or radical copolymerizable vinylic or vinyl monomers ", as used here, is intended to denote monomers which are capable of a "vinylic" polymerization or copolymerization in the presence of radical polymerization initiators to suffer.

According to one embodiment of the invention, there is a free radical polymerizable or free radical copolymerizable Vinyl monomer or such monomers in water or a aqueous medium (e.g. a mixture of water

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and methanol) and a particulate reducing inorganic substance that hardly exists in water or is not soluble at all, added and dispersed. An acid like hydrochloric acid or sulfuric acid is then used added to adjust the pH of the dispersion to 7 or less. In the event that the pH of the dispersion already at the time of the formation of the dispersion of the monomer and the particulate reducing agent inorganic substance is below 7, no special treatment is given for adjusting the pH needed. In the context of the invention, the implementation of the polymerization while maintaining a Considerable importance is attached to a pH value of less than 7. If the pH is higher than 7, it can the desired graft polymerization cannot be achieved. After adjusting the pH, it becomes water-soluble Peroxide added as a polymerization inhibitor to the dispersion and the polymerization reaction carried out under such conditions that the individual components are in intimate contact be brought together.

The graft polymerization of the monomer or monomers is carried out in this way on the surface of the inorganic Substance required while achieving a graft polymer composition with the inorganic substance as the core material.

Vinyl monomers useful in accordance with the invention include, for example, unsaturated fatty acids such as Acrylic acid and methacrylic acid, salts of unsaturated fatty acids such as sodium acrylate and potassium methacrylate; Ester of unsaturated fatty acids such as methyl acrylate and methacrylate, ethyl

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acrylate and n-octyl methacrylate; Vinyl esters of fatty acids such as vinyl acetate, vinyl propionate, vinyl laurate and vinyl stearate; Serve like butadiene, and isoprene Chloroprene; halogenated olefins such as vinyl chloride and vinylidene chloride; Styrenes like styrene itself, m-chlorostyrene and pentachlorostyrene; heterocyclic Vinyl compounds such as 2-vinyl pyridine and other vinyl compounds v / ie vinyl isocyanate, acrylonitrile and methacrylonitrile. These monomers are commonly used individually, but can also be used in a mixture of at least two representatives if desired.

Reducing inorganic substances useful as core material in the process of the present invention include those that are hardly or not at all soluble in water and capable of reducing other compounds, but are themselves oxidizable by oxidizing agents. In particular, these include reducing inorganic substances Substances sulphites such as calcium sulphite, ttisensulphite, manganese sulphite and nickel sulphite, thiosulphates such as barium thiosulfate and silver thiosulfate, metal powder such as iron powder and zinc dust, and compounds of low-valent overlying metals such as ferrous oxide and nickel oxide (NiO). These substances are commonly in the form of powder with a particle size of 0.149 mm or less used.

Examples of polymerization risk initiators within the scope of the invention useful water-soluble peroxidic compounds include persulfates such as potassium persulfate, Sodium persulfate and ammonium persulfate, hydrogen peroxide and ammonium peroxide.

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The individual components are used in the inventive method in the following ratios:.... 10-200 wt%, preferably 20-100 wt% Monome res per 100 wt% of inorganic substance and 0.01-20% by weight, preferably 0.1 10% by weight of peroxide or peroxidic compound per 100% by weight of monomer.

The comet material obtained according to the invention of inorganic substance and organic polymer may or may also be suitable as such for molding purposes can be used as a filler for other molding compounds such as plastics.

The following are examples to illustrate the invention.

example 1

Mm 200 g of calcium sulfite of 0,149 g or ringerer particle size were suspended at 50 ⁰ C under normal pressure in 800 g of water and added to the suspension with 50 g of monomeric methylmethacrylate. Then 5.0 g of potassium persulfate was added to the suspension and the mixture reacted for 6 hours. The reaction mixture was subjected to treatments including filtration, washing with methanol and drying, whereby 222.0 g of a solid material were obtained.

Extraction of polymethyl methacrylate formed as a by-product with benzene from the solid material obtained gave 199.0 g of a graft polymer composition. When a part of the graft polymer composition was decomposed with 10% hydrochloric acid, a hydrochloric acid-insoluble portion of 3.4 % was obtained. That

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IR absorption spectrum of both the benzene extract (portion extracted from benzene) as well as the portion insoluble in hydrochloric acid was practically identical to that of Polymethyl methacrylate identical. It was also found that the portion insoluble in hydrochloric acid in benzene was soluble.

These results show that the solid material the inorganic substance with grafted polymers and the homopolymer and that the benzene extract residue is formed by the inorganic substance with grafted polymers.

Example 2

20.6 g of calcium sulfite of 0.149 mm or smaller particle size were ^{suspended in 80.0 g of water at 50 °} C. under normal pressure, and 19.4 g of monomeric styrene were added to the suspension. 0.27 g of potassium persulfate in 20.0 g of water was added and the mixture was stirred for 4.5 hours and then filtered. The filtration residue was dried under reduced pressure to obtain 23.9 g of a solid material. The infrared absorption spectrum analysis of a part of the solid material showed that it was composed of calcium sulfite and polystyrene.

In a 24-hour extraction of 10 g of the solid material with a benzene benzene extract of 13 _f 2% was obtained. The extraction residue was decomposed with 10% hydrochloric acid for 2 hours, with 7.3 % material being insoluble in hydrochloric acid, which was identified as polystyrene by infrared absorption spectrography.

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Example 3

As in Example 2 80 g of water, 20.0 g of said Sulfitpulvers * (particle size of 0.149 mm or less) and 10.0 g of the above-mentioned monomers in a 200 ml three-necked flask accommodated in a constantly maintained at 50 ⁰ C Tenroeraturbad dived. To the mixture, 0.21 g of potassium persulfate dissolved in 20.0 g of water was added with stirring, and the mixture was reacted for 5 hours. The suspended reaction mixture was filtered and the solid material was ^{dried to constant weight at 50 °} C. under reduced pressure. The infrared absorption spectrum analysis of a part of the resulting solid material showed that it consisted of the sulfite and a polymer of the monomer used.

In a 24-hour extraction of 10 g of the solid ^{IVL r} at rials with benzene, a benzene extract was obtained in an amount tabulated. After the extraction residue was decomposed for 24 hours with 10% hydrochloric acid, a hydrochloric acid-insoluble material was obtained in an amount indicated in the table below. The infrared absorption spectrum analysis of the hydrochloric acid insoluble material showed that it was a polymer of the monomer used.

The amounts of sulfite and monomers used in this example and the amounts of polymers in the product are shown in the table below.

* see table on page 9

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Experiment sulfite monomer product Proportion of the HCl-insoluble part of the extract with proportion of benzene

polymeric material that

was not extracted with benzene

1 FeSO, MMA 25, 8th G 20th , 5 96 7, 4 % 2 MnSO, St. 21 3 G 5 , 6 % 3, Tt Q /
.> 7 " 3 NiSO, MMA 25, 0 G 20th ,8th % 2, Q al
Ö / D

Note: MMA means methyl methacrylate and styrene.

Example 4

As in Example 2, there was 80 grams of water, 20.0 grams powdered barium thiosulfate of 0.149 mm or less Particle size and 10.0 g of monomeric methyl methacrylate placed in a 200 ml three-necked flask which was immersed in a temperature bath kept constant at 50.degree. To the mixture, 0.20 potassium persul'a ^ t, dissolved in 20.0 g of water, and the mixture was then reacted for 6.5 hours. The sluggish one Reaction product was collected by filtration and dried to constant weight under reduced pressure, whereby 23.5 g of a solid material was obtained. The IR absorption spectrum analysis of a part the solid material showed that it was polymethyl methacrylate contained.

Extraction of 10 g of the solid material with benzene for 24 hours gave a benzene extract of 16.2 % . The extraction residue was decomposed with 10% hydrochloric acid for 2 hours, and the hydrochloric acid-insoluble material was dried under reduced pressure

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Extracted with benzene for 24 hours to obtain an extract of 6.0 %. The IR absorption spectrum analysis of the extract showed that it was formed by polymethyl methacrylate.

Example 5

As in the case of Example 2 80 g of water, 20.0 g of metallic zinc powder were (0.149 mm or smaller particle size) and 10.0 g methyl methacrylate monomer in a 200 ml three-necked flask, which appeared in a constant temperature bath maintained at 50 ⁰ C. To the mix

0.20 g of potassium persulfate dissolved in 20.0 g of water was added with stirring, and the mixture was then reacted for 6 hours. The reaction product was collected by filtration and then ^{dried to constant weight at 50 °} C. under reduced pressure, whereby 23.8 g of a solid material were obtained.

Upon extraction of 10.0 g of the solid material with benzene for 24 hours, 12.2 % was extracted by benzene. The extraction residue was decomposed with 10% hydrochloric acid to obtain 4.2 % of a material insoluble in hydrochloric acid. The infrared absorption spectrum analysis of the insoluble material showed that it was formed by polymethyl methacrylate.

Example 6

As in the case of Example 2, 80 g of water, 20.0 g of metallic iron powder (0.149 mm or less Particle size) and 10.1 g of monomeric methyl methacrylate \ Lt placed in a 200 ml three-necked flask which was immersed in a temperature bath kept constant at 50.degree. To the mixture, 0.20 g of potassium

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persulfate, dissolved, in 20.0 g of water, added and the mixture was then reacted for 6 hours. The reaction product was collected by filtration and dried under reduced pressure to constant weight, thereby obtaining 24.7 g of a solid material became.

A benzene extract of 13.1% was obtained after a 24-hour extraction of 10 g of the solid material with benzene. The IR absorption spectrum analysis of the benzene extract showed that it was formed by polymethyl methacrylate. When the extraction residue was decomposed in 10% hydrochloric acid, a 6.3% shark insoluble in hydrochloric acid was obtained. The infrared absorption spectrum analysis of the insoluble material showed that it was also polymethyl methacrylate.

Example 7

As in the case of Example 2 80 g of water, 20.0 g Ferrooxidpulver were (0.149 mm or smaller particle size) and 10.0 g methyl methacrylate monomer in a 200 ml three-necked flask, which appeared in a constant temperature bath maintained at 50 ⁰ C. To the mixture, 0.23 g of potassium persulfate dissolved in 20.0 g of water was added with stirring, and the mixture was then reacted for 5 hours. The reaction product was collected by filtration and dried under reduced pressure to constant weight, whereby 26.8 g of a solid material were obtained.

Extraction of 10 g of the solid material with benzene for 24 hours gave a benzene extract of 23.9 %

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obtain. The extraction residue was decomposed for 2 hours with 10% hydrochloric acid to give 3.h % of a material insoluble in hydrochloric acid. The IR absorption spectrum analysis of the insoluble
Materials showed it was polymethyl methacrylate.

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Claims (3)

Claims 1. Process for grafting organic polymers on inorganic substances, characterized that one has a reducing inorganic substance in particulate form which has little or no in Water soluble, suspended in an aqueous medium, is free radical polymerizable or free radical copolymerizable Contains monomers and then to the aqueous medium a water-soluble peroxide (or such a peroxidic Compound) is added at a pH of at most and thereby carries out the graft polymerization. 2. The method according to claim 1, characterized in that that the reducing inorganic substance by a sulfite or thiosulfate or a metal or a compound a low-valent transition metal is formed. 3. The method according to claim 1 or 2, characterized in that the peroxidic compound is persulfate is used. 309836/1117 ORIGINAL INSPECTED