FI61502B - BOTTLE SAMPLE SAMPLING FOR AROMATIC FUELING WITH FRAMSTAELLNING AND ANALYSIS - Google Patents

Description

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Patent · och registerrtyreieen Amekan utiagd och uti.tkrift «n pubticarad (32) (33) (31) Claim claimed privilege —Begird prlorltet 19-03-75 Bulgaria-Bulgarien (BG) 29367 (71) Kolophonen Savod" Kristall ", Velingrad, Bulgaria-Bulgarien (BG) (72) Ivan Stojanov Sarbov, Sofia, Stilijan Petkov Pentschev, Sofia,

Ljubomir Antschev Filipov, Sofia, Trajan Borissov Hristov, Sofia,

Velislav Hristov Vatov, Velingrad, Georgi Angelov Belitschinov,

The present invention relates to aromatic unsaturated compounds, to the preparation and use of unsaturated aromatic compounds, to the preparation and use of unsaturated aromatic compounds. which is well suited for the manufacture of a paper sizing agent for use in the paper industry, as well as the manufacture and use of a polymer.

A process for the preparation of modified hydrocarbon resins which are well suited for the preparation of a paper sizing agent used in the paper industry is known in which an aliphatic-aromatic hydrocarbon resin of the type obtained by copolymerizing olefinic and vinylaromatic hydrocarbons is maleinized. It is possible to obtain a water-soluble paper sizing agent from a maleinized resin only by saponification with potassium hydroxide when sodium hydroxide is unsuitable for use. According to the Cob method, the sizing ability of this paper sizing agent (at 80 ° C when the sizing agent is 1% by weight) is in the range of 31.8 to 33.1 s.

A disadvantage of the known methods is that the production of good maleinized hydrocarbon resins which are well suited for the production of high-quality, water-soluble paper sizing agents requires two fractions, Team olefinic and vinyl aromatic. The process is a two-step process and only expensive potassium hydroxide can be used to make the water-soluble paper sizing agent.

It is essential for the copolymer according to the invention that it contains the following groups, statistically distributed: ^ 1? H3 -CH ---- CH ^ T "CH2" I ru> CH2 JL T 2 CH ---- CH

[o] (oi cfl ~~ CH2 ~ CH

1 i i i> ch2 L J-o

L J Ι5Ή <> L ° J

wherein R may be hydrogen, potassium or sodium, and the copolymer may contain as end groups indene, m-vinyltoluene, N-methylstyrene, dicyclopentadiene, styrene or maleic anhydride and has a molecular weight measured by 2 cryoscopic methods between 8 x 10-120.

The above-mentioned structural properties of the copolymer have been elucidated by studies.

Analysis of the original aromatic Cg fraction (150-200 ° C) and the unreacted hydrocarbons remaining in the separation of the copolymer by gas chromatography revealed that the following monomeric molecules were mainly involved in the copolymerization: indene, m-vinyl litholuene, methylmethylene, styrene and styrene. Based on the determination of the molecular weight by cryoscopic analysis and the gas chromatographic analysis of the Cg fraction (150-200 ° C) and unreacted hydrocarbons, it was found that the copolymer contains 7-11 monomeric groups with the following numbers of groups: indene up to 4, m-vinyltoluene up to 3, , cis-methylstyrene and styrene not more than 2.

M

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Based on the infrared spectrum of resin acid, it has been found that the macromolecule contains maleic anhydride with an open ring in 40-60% of the macromolecules and closed in 40-60% of the macromolecules.

Based on the infrared spectrum, bromine number and molecular weight, it has been found that the copolymer is unsatisfactory in nature. The double bonds are due to end groups and dicyclopentadiene.

A copolymer of unsaturated aromatic compounds, which is well suited for the preparation of the high-grade paper sizing agent required by the paper industry, can be prepared by copolymerizing the Cg fraction (150-200 ° C) and maleic anhydride at atmospheric pressure at about 40-100 ° C and using L as the catalyst. 3-3% of the Cg fraction, where the Lewis acid may be aluminum chloride, boron trifluoride or titanium tetrachloride, with a ratio of maleic acid to Cg fraction of up to 50% and a reaction time of 1-3 hours. The copolymers obtained in the various experiments are aromatic thermoplastics in nature with the following physicochemical properties: 2 2 1. Molecular weight - 8 x 10-12 x 10 as measured by cryoscopic method.

2. Softening temperature - 70-100 ° C (ball-and-ring method).

3. Color according to the iodine scale - 100-636.

4. Bromine number - 25-35.

5. Acid number, mg KOH / g - more than 35.

6. Ignition temperature - above 230 ° C.

The copolymers obtained are saponified with sodium or potassium hydroxide, either as such or in the presence of rosin, and each time a water-soluble paper sizing agent is obtained which has a sizing capacity in the range of 30 to 33 by the Cob method at 80 ° C and using an amount of sizing agent of 1% by weight. p.

The physicochemical properties of the Cg fraction (150-200 ° C) used in the copolymerization with maleic anhydride are as follows: 1. Density - 0.874-0.937 g / cm 2.

2. Molecular weight - 121-138.

3. Bromine number - 82-120.

4. Gas chromatographic analysis: styrene 2.8-3.7% c-methylstyrene 4.4-6.0% vinyltoluene 15.0-18.0% indene 12.0-18.0% dicyclopentadiene 4.2-5 .3%.

4 61502 100% missing contains xylenes, pseudocoumene and other unidentified compounds.

The advantages of the obtained copolymer are aromaticity (only Cg fraction is used) and very good sizing properties. Production requires one less preparation step compared to other known methods, and sodium hydroxide can be used in the preparation, which is available more advantageously than potassium hydroxide. This copolymer replaces the naturally occurring and expensive natural rosin (rosin) in the aqua-lentic way in the production of the paper sizing agent needed by the paper industry.

The following examples further illustrate this invention.

Example 1 300 g of Cg fraction and 60 g of maleic anhydride are added to a 1 liter three-necked flask equipped with a stirrer, thermometer and burette. The copolymerization uses 5.0 g of complex catalyst (AlCl 3 content 2.5 g), a reaction temperature of 60 ° C and a reaction time of 1 hour. The complex catalyst is prepared from aluminum chloride and an aromatic solvent by adding a certain amount of water. The catalyst is decomposed by adding 100 g of water to form two layers, the upper being the aqueous layer and the lower being the resin layer. Evaporation of unreacted hydrocarbons from the resin layer gives a maleinized hydrocarbon resin having the properties shown in Table 1.

Example 2

Otherwise the same as Example 1, but using a temperature of 50 ° C and a reaction time of 2 hours.

Example 3

Otherwise the same as in Example 1, but using 100 g of maleic anhydride, a reaction time of 3 hours and boron fluoride as catalyst.

Example 4

Otherwise the same as Example 1, but using 80 g of maleic anhydride, 6.0 g of complex catalyst (AlCl 2 content 3 g) and a reaction time of 2 hours.

Example 5

Otherwise the same as in Example 1, but using titanium nitretrachloride as a catalyst at 45 ° C and no rosin in the saponification.

Example 6

Otherwise the same as Example 1, but using 4.5 g of catalyst complex (AlCl 2 content 2.25 g) at 65 ° C and a reaction time of 3 hours.

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Example 7

The resins prepared in the above examples are saponified using 45% sodium hydroxide or 45% potassium hydroxide. The sizing ability of the obtained paper sizing agents was tested by the Cob method at 80 ° C with an amount of sizing agent of 1% by weight. The results are shown in Table 2. m. ,,.

table 1

Properties Example No. 1 2 3 4 5 6 1 Molecular weight 950 900 1 040 1 100 950 980 2 Acid number (mg KOH / g) 35.7 76.5 90.6 90.6 38.5 65.6 3 Bran number ( g Br / 100) 30.0 28.0 30.0 32.0 26.0 30.0 4 Softening temperature (° C) (ball-and-ring method) 80 75 82 85 76 78 5 Color according to the iodine scale 250 300 200 200 300 400 6 Svtt-vmi «temperature (° C) __ 230 235__240__240 230__235_

Table 2

Resin obtained in Example No. Sizing ability in seconds according to the Oob method at 80 ° C with an amount of sizing agent of 1% by weight

Sizing agent made with sodium hydroxide Sizing agent made with potassium hydroxide sizing agent 1 32.5 32.0 2 31.0 30.5 3 30.5 30.0 4 30.0 30.0 5 32.0 31.0 6 31.5 31.5

Claims (3)

6 61502 Copolymer of unsaturated aromatic compounds, characterized in that it contains, statistically distributed, the following groups: CK3 CH ---- CH2-CH-CH-- -C-CH- »I Γ 2 2 CH ---- CH 2 2 _0 J 10 J -CH ----- CH- -CH-CHo ~ CH CH “CH CH- III ch II COOR COOR foi s' ...... 2 C \ 9 ° J ch3 [0 where R may be hydrogen, potassium or sodium, and the copolymer may contain as end groups indene, m-vinyltoluene, c (methylstyrene, dicyclopentadiene, styrene or maleic anhydride) and its molecular weight measured by cryoscopic method is between 8 x 10 -12 x . Process for the preparation of a copolymer according to Claim 1, characterized in that a C8 fraction having a boiling point of 150 to 200 ° C and maleic anhydride at atmospheric pressure at a reaction temperature of 40 to 100 ° C and Lewis acid, which may be aluminum chloride, boron trifluoride, is copolymerized or titanium titr chloride. Use of a copolymer according to claim 1, wherein R represents sodium or potassium, either as such or, if desired, with rosin in the paper industry as a paper sizing agent.