CN1091751A - Water-soluble carbon pellet petroleum resin - Google Patents

Abstract

C9 water-soluble petroleum resin is a solution free radical copolymerization (including solution homogeneous copolymerization and solution precipitation copolymerization) or free radical emulsion copolymerization of the by-product C9 distillate oil produced from ethylene and A; the copolymerized product is saponified , and made. Wherein A can be acrylic acid, acrylate ester, acrylonitrile, acrylamide, maleic anhydride, maleic acid ester or vinyl acetate. The carbon nine water-soluble petroleum resin can be used as oilfield water quality stabilizer, drilling mud high-temperature diluent, thickener and other oilfield chemical agents.

Description

The present invention relates to a water-soluble _C9 petroleum resin, in particular to a copolymer of a polymerizable component having a double bond and a vinyl polar monomer in the by-product _C9 fraction of ethylene production and the copolymer obtained by saponification of the copolymer A water-soluble _C9 petroleum resin, a method for producing the water-soluble _C9 petroleum resin, and a chemical agent for oilfields such as a drilling mud high-temperature diluent and an oilfield water quality stabilizer.

At home and abroad, the C ₉ fraction has been regarded as the raw material for the production of oil-soluble C ₉ aromatic hydrocarbon petroleum resins. Oil-soluble C ₉ aromatic petroleum resins have been widely used in packaging, papermaking, printing, rubber, paint, transportation and other industries at home and abroad. Although oil-soluble C ₉ petroleum resins have been developed and applied earlier than the 1940s, in recent years, In order to meet and expand the application, on the basis of continuously improving product quality, vigorously carry out modification, mainly by copolymerizing the polymerizable components with double bonds in the _C9 fraction with other copolymerizable monomers to improve and increase the _C9 The performance of petroleum resin is suitable for many purposes.

US4539388 discloses the modified _C9 petroleum resin which improves its heat resistance by copolymerization of unsaturated polymerizable aromatic hydrocarbon components and aromatic carboxylic acid in the presence of Friedel-Crafts catalyst in the _C9 fraction, but it is oil-soluble Modified _C9 petroleum resin. EP348975A discloses that the polymerizable components in the C _fraction and maleic anhydride carry out radical copolymerization to obtain an oil-soluble copolymer resin, and a salt of the carbonized product of the copolymer resin, which is water-soluble. EP393685A discloses a copolymer prepared by free-radical copolymerization of the polymerizable components in the _C9 fraction and maleimide to improve the heat resistance of the _C9 petroleum resin and used as a resin modifier. The above-mentioned modified _C9 petroleum resins contain low content of polar groups, and the distribution is uneven, and they are oil-soluble copolymers, even if they are water-soluble, they are also sulfonated products.

The object of the present invention is to provide a complete product obtained through free radical alternating copolymerization and saponification of the polymerizable component having a double bond in the by-product _C9 fraction of ethylene production (hereinafter referred to as the _C9 fraction) and vinyl polar monomer. Water-soluble _C9 petroleum resin. Another object of the present invention is the method for producing water-soluble _C9 petroleum resin by free radical solution copolymerization or emulsion copolymerization and by water-soluble _C9 petroleum resin of the present invention is used as oil field drilling mud high temperature diluent and oil field stabilizer etc. Chemicals.

The water-soluble _C9 petroleum resin of the present invention is a saponification product of a copolymer of a polymerizable component having a double bond and a vinyl polar monomer in the by-product _C9 fraction of ethylene production, wherein the copolymer is an alternating copolymer with a molecular weight of ≥6000, the chain link of vinyl polar monomer in the copolymer is 30-50% (mol).

The water-soluble _C9 petroleum resin of the present invention can carry out free radical solution copolymerization (including solution homogeneous copolymerization and solution precipitation) by the polymerizable component with double bond in the by-product _C9 fraction of ethylene production and vinyl polar monomer Copolymerization) or carry out free radical emulsion copolymerization, and then directly saponify the copolymerized product with alkali to prepare.

Fig. 1 is the preparation process chart of water-soluble _C9 petroleum resin of the present invention, wherein _C9 is the component unit that has double bond polymerizable in the _C9 fraction, n is the repeating unit number that makes its molecular weight ≥ 6000, and A is ethylene base polar monomer unit.

The boiling range of the by-product _C9 fraction used in the present invention is generally 80-220°C, and its main components include some aromatic compounds without reactive double bonds, such as benzene, toluene, xylene, trimethylbenzene, ethyl Toluene, indane, tetramethylbenzene, methylindane, propylbenzene, and naphthalene, etc.; and polymerizable components with reactive double bonds such as styrene, alpha-methylstyrene, methylstyrene, Dimethylstyrene, trimethylstyrene, indene, methylindene, dicyclopentadiene, coumar, etc., the content of polymerizable components with reactive double bonds in the _C9 fraction is generally 20-80% ( weight), preferably 40-60% (weight).

The vinyl polar monomer of the present invention is selected from acrylic acid, acrylate ester, acrylonitrile, acrylamide, maleic anhydride, maleic acid ester, vinyl acetate, preferably acrylic acid or its ester, acrylonitrile , preferably acrylic.

The radical initiators used in the copolymerization process are peroxides or azo compounds. The peroxide is dibenzoyl peroxide, dipicryl peroxide, tert-butyl perbenzoate, 1,4-bis-tert-butyl peroxycumyl peroxide, perbenzoic acid, tert-butyl etc., preferably Benzoyl peroxide. Azo compounds are azobisisobutyronitrile and azobiscyclohexanenitrile.

The solvent used in the copolymerization process of the present invention is alcohols, such as methanol, ethanol, propanol, isopropanol, ketones, such as acetone, methyl ethyl ketone; Esters, such as ethyl acetate, methyl acetate; or benzene, toluene Or any single solvent in aromatic hydrocarbons such as mixed aromatic hydrocarbons; it can also be a mixed solvent composed of these solvents.

The alkali used in the saponification process of the present invention is any one of NaOH, KOH, NH ₃ H ₂ O (ammonia water), and Na ₂ CO ₃ .

If the emulsion copolymerization solvent is water, the emulsifier is OP-10.

Implement the concrete scheme of the present invention as follows:

1. Copolymerization by free radical solution

Use the double bond polymerizable components in the ethylene by-product _C9 fraction to carry out free radical solution copolymerization (including solution homogeneous copolymerization and solution precipitation copolymerization) with vinyl polar monomers. The polymerizable active ingredients in the _C9 fraction are Account for 20-80% (by weight) in the reactant, preferred range is 40-60%, the ratio of polymerizable active ingredient and vinyl polar monomer in the C ₉ fraction makes it 30-50% (mol) in the copolymer, The volume ratio of _C9 fraction to solvent is 1:1-10. Solvents can be alcohols, such as methanol, ethanol, propanol, isopropanol, etc.; esters, such as ethyl acetate, methyl acetate, etc.; ketones, such as acetone, butanone; or aromatics, such as benzene, toluene, mixed Any single solvent in aromatic hydrocarbons; it can also be a mixed solvent composed of them, such as ethanol: butanone: benzene = (1-7): (4-1): (5-2) (volume ratio), acetic acid Ethyl ester: acetone: toluene=(3-6): (5-1): (2-3) (volume ratio), methanol: butanone: mixed aromatics=(2-4): (6-1): ( 5-2) (volume ratio), ethanol: butanol = (1-7): (9-3) (volume ratio), ethyl acetate: acetone = (5-8): (5-2) (volume ratio ), acetone: mixed aromatics = (3-5): (7-5) (volume ratio), butanone: benzene = (6-8): (4-2) (volume ratio) and so on. In the copolymerization, peroxides such as benzene peroxide or azo compounds such as azobisisobutyronitrile can be used as initiators; the reaction temperature is 50-140 ° C, and the preferred range is 50-100 ° C; the copolymerization reaction The time is 1-8 hours, preferably 1-5 hours. The solvent and residual oil of the distillate are separated by vacuum distillation to obtain a C ₉ -A copolymer.

2. By free radical emulsion copolymerization

Carry out free radical emulsion copolymerization with the double-bond polymerizable components in the by-product _C9 fraction of ethylene production and vinyl polar monomers, and the polymerizable active ingredient in the _C9 fraction is 20-80% (weight), preferably The range is 40-60% (weight), the solvent is water, and the volume ratio of _C9 fraction to water is 1:1-10. The emulsifier is OP-10, and its dosage is 0.1-1% (by weight). The initiator is a peroxide such as benzoyl peroxide, or an azo compound such as azobisisobutyronitrile, the reaction temperature is 50-100°C, and the reaction time is 1-8 hours, preferably 1-5 hours .

In the C ₉ -A copolymer obtained by method 1 and method 2, the A chain segment is 30-50% (mole), the yield of the C ₉ -A copolymer is 39-80%, and the molecular weight is ≥ 6000.

3. Saponification

Water-soluble _C9 petroleum resin can be obtained by reacting the C ₉ -A copolymer obtained from method 1 or method 2 with alkali in an appropriate amount of water at 60-100°C for 1-5 hours. The base is selected from NaOH, KOH, NH ₃ H ₂ O or Na ₂ CO ₃ . Wherein the weight ratio of the C ₉ -A copolymer to the base is 1: (1-3). The obtained water-soluble _C9 petroleum resin is completely soluble in water, and the yield is 100%.

The present invention further illustrates the present invention with the following examples, but does not limit the present invention.

Example 1

In a vessel equipped with a stirrer, reflux condenser and thermometer, 19 ml of C9 distillate, 63 ml of vinyl acetate and 190 ml of ethanol were added. Add 4.0 g of azobisisobutyronitrile at 50°C and react for 1 hour to obtain a carbon nona-vinyl acetate copolymer with a yield of 75% and a molecular weight of 7000.

Example 2

In a container equipped with a stirrer, a reflux condenser and a thermometer, add 38ml of C9 fraction oil, 48g of acrylamide and 260ml of a mixed solvent composed of ethanol, methyl ethyl ketone and benzene, wherein 26ml of ethanol, 104ml of methyl ethyl ketone, and 130ml of benzene ; Or ethanol 182ml, butanone 26ml, benzene 52ml. At 70°C, 2.4 g of azobisisobutyronitrile was added and reacted for 2 hours to obtain a C9-acrylamide copolymer with a yield of 65% and a molecular weight of 6500.

Example 3

In a container equipped with a stirrer, a reflux condenser and a thermometer, add 48ml of C9 distillate oil, 40g of maleic anhydride and 200ml of a mixed solvent composed of ethanol, methyl ethyl ketone and mixed aromatics (wherein methanol 40ml, methyl ethyl ketone 120ml, mixed aromatics 40ml; or methanol 60ml, butanone 40ml, mixed aromatics 100ml). Add 0.8 g of benzoyl peroxide at 140° C. and react for 5 hours to obtain a carbon nine-maleic anhydride copolymer with a yield of 40% and a molecular weight of 8,000.

Example 4

In the container that agitator, reflux condenser and thermometer are housed, add 57ml carbon nine fraction oil, 49ml acrylic acid ester and 180ml the mixed solvent that is made up of ethyl acetate, acetone and toluene, wherein ethyl acetate 54ml, acetone 90ml, Toluene 36ml; or ethyl ester 108ml, acetone 18ml, toluene 54ml. At 100°C, 0.4 g of formyl peroxide was added and reacted for 5 hours to obtain a C9-acrylic acid copolymer with a yield of 80% and a molecular weight of 7500.

Example 5

In the container that agitator, reflux condenser and thermometer are housed, add 67ml of carbon nine fraction oil, 61g of maleic acid ester and 200ml of the mixed solvent that is made up of ethyl acetate and mixed aromatics, wherein ethyl acetate 60ml, Mixed aromatics 140ml; or ethyl acetate 120ml, mixed aromatics 80ml. At 120°C, 0.2 g of benzoyl peroxide was added and reacted for 7 hours to obtain a carbon nine-maleic acid ester copolymer with a yield of 75% and a molecular weight of 9000.

Example 6

In a vessel equipped with a stirrer, reflux condenser and thermometer, 77 ml of C9 distillate, 20 ml of acrylic acid and 80 ml of acetone were added. At 60°C, 0.08 g of azobisisobutyronitrile was added and reacted for 8 hours to obtain a carbon nine-acrylic acid copolymer with a yield of 60% and a molecular weight of 6000.

Example 7

In a vessel equipped with a stirrer, reflux condenser and thermometer, 48ml of C9 distillate, 40g of maleic anhydride and 144ml of H ₂ O and 5g of OP-10 emulsifier were added. At 80°C, 0.4g of BPO was added and reacted for 3 hours to obtain a carbon nine-maleic anhydride copolymer with a yield of 40% and a molecular weight of 7500.

Example 8

From the obtained carbon nine-A copolymer in example 1-example 7, one is chosen arbitrarily, in the container that agitator, reflux condenser and thermometer are housed, add 10g carbon nine-A copolymer, 10gNaOH and 200mlH ₂ O, React at 100°C for 2 hours, and separate H ₂ O by vacuum distillation to obtain water-soluble C9 petroleum resin.

Example 9

From the obtained carbon nine-A copolymer of example 1-example 7, arbitrarily choose one in the container that agitator, reflux hydrocondenser and thermometer are housed, add 10g carbon nine-A copolymer, 10gKOH and 200mlH ₂ O, in React at 100°C for 1 hour, and vacuum separate the water to obtain the water-soluble C9 petroleum resin.

Example 10

From the obtained carbon nine-A copolymer of example 1-example 7, one is chosen arbitrarily. In a container equipped with a stirrer, a reflux condenser and a thermometer, add 10g of C9-A copolymer, 100ml of concentrated NH ₃ H ₂ O and 200ml of water, react at 80°C for 4 hours, separate by vacuum distillation, and obtain a water-soluble Carbon nine petroleum resin.

Example 11

From the obtained carbon nine-A copolymer of example 1-example 7, one is chosen arbitrarily. In a container equipped with a stirrer, a reflux condenser and a thermometer, add 10g of C9-A copolymer, 20g of Na ₂ CO ₃ and 200ml of H ₂ O, react at 90°C for 5 hours, separate the water by vacuum distillation, and obtain a water-soluble Carbon nine petroleum resin.

Claims (10)

1, a kind of water-soluble C9 petroleum resin is characterized in that it being the saponification resultant that has the multipolymer of the polymerizable components of two keys and vinyl polar monomer in the by-product C9 cut of ethylene production; The alternating copolymer represented by (C9-A) n of multipolymer wherein, molecular weight is 〉=6000, vinyl polar monomer chain link is 30-50% (mole) in the multipolymer; Described vinyl polar monomer is selected from vinylformic acid, acrylate, vinyl cyanide, acrylamide, MALEIC ANHYDRIDE, maleate, vinyl acetate.

2,, it is characterized in that described vinyl polar monomer is vinylformic acid or ester according to the water-soluble C9 petroleum resin of claim 1.

3, a kind of water-soluble C9 preparation method of petroleum resin, it is characterized in that by having two key polymerizable components in the ethylene production by-product C9 cut and the vinyl polar monomer carries out radical solution copolymerization or carries out the free radical emulsion copolymerization, then copolymerization product is directly prepared with alkali soapization, wherein said C9 cut is that boiling range is generally 80-220 ℃ of cut, can be grouped to be divided into 20-80%(weight); Described vinyl polar monomer is selected from vinylformic acid, acrylate, vinyl cyanide, acrylamide, MALEIC ANHYDRIDE or ester, vinyl acetate; Described alkali is NaOH, KOH, NH ₃H ₂O, Na ₂CO ₃

4, method according to claim 3, it is characterized in that ⅰ has two key polymerizable components in the ethylene by-product thing C9 cut and the vinyl polar monomer carries out radical solution copolymerization with producing, polymerisable effective constituent is 20-80%(weight in the described C9 cut), the C9 cut is 1 with the solvent volume ratio: 1-10, solvent is an alcohols, the ester class, ketone, aromatic hydrocarbons and their mixture thereof, available superoxide or azo-compound are initiator in the copolymerization, the copolymerization temperature is 50-140 ℃, polymerization reaction time is 1-8 hour, isolate solvent by vacuum distilling subsequently, the cut residue obtains the C9-A multipolymer;

ⅱ with the C9-A multipolymer of gained and alkali in suitable quantity of water and 60-100 ℃ reaction 1-5 hour down, water-soluble fully C9 petroleum resin, yield 100%, wherein the weight ratio of C9-A multipolymer and alkali is 1: (1-3), described alkali is selected from NaOH, KOH, NH ₂H ₂O, Na ₂CO ₃

5, according to the method for claim 3, it is characterized in that ⅰ has the polymerisable component of two keys in the ethylene by-product C9 cut and the vinyl polar monomer carries out the free radical emulsion copolymerization with producing, polymerizable components is a 20-80%(weight in the C9 cut), solvent is a water, and the volume ratio of C9 cut and water is 1: 1-10, emulsifier op-10, its consumption is a 0.1-1%(weight), initiator is peroxidation oxide compound or azo-compound, and temperature of reaction is 50-100 ℃, and the reaction times is 1-8 hour;

ⅱ in suitable quantity of water and 60-100 ℃ reaction 1-5 hour down, obtains water-soluble C9 petroleum resin fully with the C9-A multipolymer of gained and alkali, and yield is 100%, and wherein the weight ratio of C9-A multipolymer and alkali is 1: (1-3), described alkali is selected from NaOH, KOH, NH ₂H ₂O, Na ₂CO ₃

6, according to the method for the arbitrary claim of claim 3-5, it is characterized in that described C9 polymerizable effective constituent is 40-60%(weight).

7,, it is characterized in that temperature of reaction is 50-100 ℃ according to the method for claim 4.

8,, it is characterized in that the reaction times is 1-5 hour according to the method for claim 4.

9,, it is characterized in that the reaction times is 1-5 hour according to the method for claim 5.

10, a kind of water-soluble C9 petroleum resin are as oil field water quality stabilizer, drilling mud high-temperature diluent, thickening material.