CN1796425A - Method for preparing polymer of butene diacid - Google Patents
Method for preparing polymer of butene diacid Download PDFInfo
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- CN1796425A CN1796425A CN 200410103526 CN200410103526A CN1796425A CN 1796425 A CN1796425 A CN 1796425A CN 200410103526 CN200410103526 CN 200410103526 CN 200410103526 A CN200410103526 A CN 200410103526A CN 1796425 A CN1796425 A CN 1796425A
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Abstract
This invention relates to a preparation method for poly(butenedioic acid). Polymerization takes places in aqueous phase where there are monomers including one of several species of butenedioic acid and its derivatives, transition metal salts as catalysts and possibly hypophosphorous acid, phosphorous acid and their salts as well. It is initiated with the addition of guanyl isopropylazo hydrochloride and oxyol and the molecular weight of the polymers is over 800. Therefore, poly (butenedioic acid) with a high molecular weight can be prepared in this method and the common problems of low molecular weight and high molecular weight distribution that exist in current techniques can be effectively solved. And the consequent polymer product performs an active scale-inhibitory and corrosion-inhibitory effect and excellent properties of complex systems.
Description
Technical field
The present invention relates to a kind of preparation method of polymkeric substance, especially a kind of molecular weight is greater than the preparation method of 800 polymer of butene diacid.
Background technology
Polymer of butene diacid and its esters can be used as dispersion agent, scale inhibitor, cleaning additive, sequestering agent etc., and wherein molecular weight is that the effect of 800～3000 polymkeric substance is more effective.
For example, the hydrolytic polymaleic anhydride of molecular weight 800～3000 (HPMA) is the Scale inhibitors of a kind of recirculated cooling water preferably and feedwater, and the high more result of use of its molecular weight is good more, HPMA and the composite use of other water treatment agent (inhibiter), can reach the purpose of scale inhibitor, have wide range of applications.
The production of polymer of butene diacid is often adopted with water to be the water method of solvent and to be the nonaqueous phase method of solvent with benzene or toluene, and the molecular weight of gained polymer of butene diacid is lower, generally below 700, has influenced the result of use of polymerisate.
Summary of the invention
The problem that the polymer of butene diacid molecular weight that exists in the prior art is lower in order to solve, molecular weight distribution is not concentrated the invention provides a kind of preparation method who utilizes hydrochloric acid amidino groups sec.-propyl azo and hydrogen peroxide as the polymer of butene diacid of initiator.
Utilize soluble transition metal salt as catalyzer, utilize hydrochloric acid amidino groups sec.-propyl azo and hydrogen peroxide as initiator, carry out polyreaction at aqueous phase, generate polymer of butene diacid, the molecular weight of polymerisate is greater than 800.Can introduce a certain amount of phosphorus in the polymerization process, make polymerisate have scale inhibition function and corrosion inhibitive function simultaneously.
Hydrochloric acid amidino groups sec.-propyl azo [2,2`-Azobis (2-amidinopropane) hydrochloride] is a kind of azo type free base initiator, and structural formula is:
The preparation method of a kind of polymer of butene diacid of the present invention is achieved in that
Polyreaction is carried out at aqueous phase; Described aqueous phase contains monomer and catalyzer, and initiator is joined this aqueous phase, carries out polyreaction.
Described monomer comprises one or more in butene dioic acid and the derivative thereof, and described derivative is maleic acid anhydride and butene dioic acid salt; Described catalyzer is one or more of transition metal salt; Described initiator is the mixture of hydrochloric acid amidino groups sec.-propyl azo and hydrogen peroxide.
The concentration of described monomer in the aqueous solution is 10～60% weight; The concentration of described catalyzer in the aqueous solution is 100～500mg/l; The add-on of described initiator hydrochloric acid amidino groups sec.-propyl azo is: greater than the 0g/mol monomer, smaller or equal to the 10g/mol monomer; The add-on of described initiator hydrogen peroxide is 9～60g/mol monomer.
The temperature of polyreaction is 60～105 ℃; The time of polyreaction is 3.0～9.0 hours.
Catalyzer is a soluble transition metal salt, and transition metal ion plays the effect of chain-transfer agent in polyreaction.Initiator is the mixture of hydrochloric acid amidino groups sec.-propyl azo and hydrogen peroxide, and free radical is provided in polyreaction, and hydrochloric acid amidino groups sec.-propyl azo plays the stability that increases free radical, the effect that improves the molecular weight of polymerisate.
Hydrochloric acid amidino groups sec.-propyl azo is a solid under the normal temperature.The method that initiator is joined aqueous phase is: at first hydrochloric acid amidino groups sec.-propyl azo is joined the aqueous phase that contains monomer and catalyzer, after the dissolving, again aqueous hydrogen peroxide solution is added drop-wise to aqueous phase; Perhaps, hydrochloric acid amidino groups sec.-propyl azo and hydrogen peroxide are mixed, after the dissolving, be added drop-wise to the aqueous phase that contains monomer and catalyzer together.
When concrete enforcement was of the present invention, described monomer was selected from: one or more in maleic acid, MALEIC ANHYDRIDE, methyl-maleic acid acid anhydride, the FUMARIC ACID TECH GRADE; Described catalyzer is selected from: one or more in the water-soluble salt of iron, copper.The kind of water-soluble transition metal salt is more, comprises vitriol, nitrate etc., and ferric sulfate, copper sulfate, ferric ammonium sulfate, iron nitrate, cupric nitrate etc. can play the effect that prolongs radical life, catalytic polymerization in polyreaction.
When concrete enforcement was of the present invention, the concentration of described monomer in the aqueous solution was 40～50% weight; The concentration of described catalyzer in the aqueous solution is 200～300mg/l; The add-on of described initiator hydrochloric acid amidino groups sec.-propyl azo is 0.1～1.0g/mol monomer; The add-on of described initiator hydrogen peroxide is 18～30g/mol monomer.
Monomer has the comparison remarkable influence at the starting point concentration of aqueous phase to the molecular weight of polymerisate, polymer molecular weight is with monomer increasing and increase at the starting point concentration of aqueous phase, but too high starting point concentration can cause the curing phenomenon in the polymerization process, influences the carrying out of polyreaction.Catalyst consumption has remarkable influence to the molecular weight of polymerisate, and this molecular weight with the increasing and increase of catalyst levels, after reaching higher level, increases catalyst consumption earlier, and the molecular weight of polymkeric substance is stabilized in a high position.The consumption of initiator has certain influence to polymer molecular weight, and this molecular weight improves with the increase of initiator amount, but too high initiator amount also can cause the decline of polymer molecular weight.
Higher temperature of reaction and suitable reaction times help the raising of polymer molecular weight.When concrete enforcement was of the present invention, the temperature of described polyreaction was 90～105 ℃; The time of described polyreaction is 3.0～6.0 hours.
When concrete enforcement was of the present invention, described monomer can also comprise: one or more in unsaturated carboxylic acid monomer, unsaturated " non-carboxylic " acid mono and the unsaturated non-acid mono beyond the butene dioic acid; In polymerization aqueous phase, the mol ratio of above-mentioned monomer total amount and butene dioic acid and derivatives monomer total amount thereof is: greater than 0, smaller or equal to 0.2.
Described unsaturated carboxylic acid monomer is selected from: one or more in vinylformic acid, methacrylic acid, the hydroxyl acrylic; Described unsaturated " non-carboxylic " acid mono is selected from: one or more in allyl sulphonic acid, allyl group phosphonic acids, the allyl group oxygen Phenylsulfonic acid; Described unsaturated non-acid mono is selected from: one or more in acrylamide, N tert butyl acrylamide, the N-vinyl pyrrolidone.
When concrete enforcement was of the present invention, also can contain in the polymerization aqueous phase: one or more in Hypophosporous Acid, 50, phosphorous acid, hypophosphite and the phosphite, its phosphorus content were 0.1～10% weight of total monomer weight; Preferred phosphorus content is 0.5～2.0% weight of total monomer weight.
Polymerization process of the present invention, be applicable to the copolymerization of the monomeric polymerization of butene dioic acid and itself and unsaturated carboxylic acid monomer, unsaturated " non-carboxylic " acid mono, unsaturated non-acid mono, the monomeric species that can carry out polyreaction is more, is characterized in monomeric nonsaturation.The purpose that adds phosphorous acid, Hypophosporous Acid, 50 or its salt in reaction is that phosphorus is introduced in the polymer of butene diacid, improves the performance of polymerisate.The transformation efficiency of phosphorus can reach more than 95.0% in the polyreaction, and it is also favourable to the molecular weight that improves polymkeric substance to add an amount of phosphorus.
The solid content of polymerisate is 10～50% weight.The consumption of polymeric reaction temperature, polymerization reaction time, initiator is bigger to the influence of solid content, and the content of catalyzer and phosphorus is less to the influence of solid content.
The molecular weight that utilizes the polymer of butene diacid that this preparation method obtains can be used as anti-incrustation corrosion inhibitor greater than 800, is widely used in fields such as industrial circulating cooling water and oil field reinjection water, has scale inhibition function, corrosion inhibitive function and good compound property.
Preparation method of the present invention has solved the problem that the polymer of butene diacid molecular weight is low in the prior art, molecular weight distribution is not concentrated.By selecting suitable initiator and polymeric reaction condition for use, obtained molecular weight greater than 800 polymer of butene diacid, the molecular weight distribution of polymkeric substance is concentrated; In polymerization process, do not need to add the alkali neutralization, simplified the process of polyreaction.
Embodiment
Be described in further detail technical scheme of the present invention below in conjunction with embodiment, protection scope of the present invention is not limited to following embodiment.
The analytical procedure that adopts in embodiment and the Comparative Examples is respectively:
● the polymer molecule quantity measuring method
Adopt the molecular weight of each sample of gel chromatography, standard model is eight acetyl glucose.
● polymkeric substance phosphorus content measuring method
Adopt industry standard ZB/T G76 002-90, measure total inorganic phosphorus (TIP), total phosphorus (TP), organophosphorus (TOP) content of each sample, calculate the transformation efficiency (P%) of phosphorus.
● polymerisate determination of solid content method
Solid content (W/W%) with the gravimetric determination polymerisate.
● the compound property test method
Get polymerisate and mix, deposited 6 months, observe the changing conditions of its solution appearance with a certain proportion of inhibiter PAPE, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid.
● the scale-inhibiting properties test method
Adopt chemical industry standard HG/T 2024-91 " water treatment agent scale-inhibiting properties measuring method--Bubbling method ".
● the corrosion inhibition test method
Adopt chemical industry standard HG/T 2159-91 " mensuration of water conditioner corrosion inhibition--rotary hanging plate method ".
Reagent and the specification thereof used in embodiment and the Comparative Examples are respectively:
● monomer
The MALEIC ANHYDRIDE SILVER REAGENT is commercially available
Methyl-maleic acid acid anhydride SILVER REAGENT is commercially available
The vinylformic acid SILVER REAGENT is commercially available
Propenyl sulfonic acid SILVER REAGENT is commercially available
The acrylamide SILVER REAGENT is commercially available
● catalyzer
The ferric ammonium sulfate analytical pure is commercially available
The copper sulfate analytical pure is commercially available
● initiator
Hydrogen peroxide assay pure (30% aqueous solution)
Hydrochloric acid amidino groups sec.-propyl azo Japan Wako company's product (V50)
● phosphorization agent
The Hypophosporous Acid, 50 analytical pure is commercially available
The phosphorous acid analytical pure is commercially available
● water distilled water
Embodiment 1
The preparation of polymer of butene diacid
Polyreaction is carried out at aqueous phase.Polymerization reactor is a four-hole boiling flask that heating unit, condensation reflux unit, whipping appts and thermometer are housed.
Add monomer, catalyzer and water in four-hole boiling flask, solid materials heats to temperature of reaction after dissolving fully, drips initiator and begins polyreaction, stops heating behind the certain hour, and reactant is cooled to normal temperature, obtains polymerisate.
Monomer is a MALEIC ANHYDRIDE, and catalyzer is a ferric ammonium sulfate, and initiator is hydrochloric acid amidino groups sec.-propyl azo and hydrogen peroxide.
The concentration of monomer in the aqueous solution is 40% weight, and the concentration of catalyzer in the aqueous solution is 200mg/L, and the add-on of initiator hydrochloric acid amidino groups sec.-propyl azo is the 1.0g/mol monomer, and the add-on of initiator hydrogen peroxide is the 30g/mol monomer; Also contain Hypophosporous Acid, 50 in the polymerization aqueous phase, its phosphorus content is 1.0% of a total monomer weight.
The adding method of initiator is: hydrochloric acid amidino groups sec.-propyl azo is joined (concentration is 30% weight) in the aqueous hydrogen peroxide solution, after the dissolving, be added drop-wise to the aqueous phase that contains monomer and catalyzer together fully.
The temperature of polyreaction is 90 ℃, and the time of polyreaction is 6.0 hours.
The number-average molecular weight of the polymer of butene diacid that polyreaction obtains is 980, and the molecular weight distribution coefficient is 1.28.
Polymerisate and performance measurement
This polymeric reaction product is that main chain is the phosphorous polymer of maleic acid, and its structural formula is as follows:
Wherein R1 is:
Polymerisate is the red-brown transparent liquid, and proportion 1.15, the solid content of polymkeric substance are that 48% weight, phosphorus content are 1.0% weight.
Compound property test: polymerisate can not change outward appearance with any ratio and inhibiter PAPE, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid uniform mixing, and compatibility is good.
The scale-inhibiting properties test: polymerisate has good scale-inhibiting properties, and the dirt of formation is loose floating, stablizes Ca
2+Concentration can reach 27.45mg/l.
Corrosion inhibition test: polymerisate has certain corrosion inhibition when using separately, with other water conditioners when composite corrosion inhibition better (for example: 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid), corrosion inhibition rate can reach 99.2%.
Embodiment 2
Polymerization reactor is identical with embodiment 1 with polymerization process.
The monomer of polyreaction is that MALEIC ANHYDRIDE, catalyzer are that ferric ammonium sulfate, initiator are hydrochloric acid amidino groups sec.-propyl azo and hydrogen peroxide.
The concentration of monomer in the aqueous solution is 10% weight, and the concentration of catalyzer in the aqueous solution is 100mg/L, and the add-on of initiator hydrochloric acid amidino groups sec.-propyl azo is the 0.1g/mol monomer, and the add-on of initiator hydrogen peroxide is the 9g/mol monomer; Also contain phosphorous acid in the polymerization aqueous phase, its phosphorus content is 0.1% of a total monomer weight.
The adding method of initiator is: hydrochloric acid amidino groups sec.-propyl azo is joined (concentration is 30% weight) in the aqueous hydrogen peroxide solution, after the dissolving, be added drop-wise to the aqueous phase that contains monomer and catalyzer together fully.
The temperature of polyreaction is 60 ℃, and the time of polyreaction is 3.0 hours.
The number-average molecular weight of the polymer of butene diacid that polyreaction obtains is 810.
Embodiment 3
Polymerization reactor is identical with embodiment 1 with polymerization process.
The monomer of polyreaction is that MALEIC ANHYDRIDE, catalyzer are that ferric ammonium sulfate, initiator are hydrochloric acid amidino groups sec.-propyl azo and hydrogen peroxide.
The concentration of monomer in the aqueous solution is 60% weight, and the concentration of catalyzer in the aqueous solution is 500mg/L, and the add-on of initiator hydrochloric acid amidino groups sec.-propyl azo is the 10g/mol monomer, and the add-on of initiator hydrogen peroxide is the 60g/mol monomer; Also contain Hypophosporous Acid, 50 in the polymerization aqueous phase, its phosphorus content is 10% of a total monomer weight.
The adding method of initiator is: at first hydrochloric acid amidino groups sec.-propyl azo is joined the aqueous phase that contains monomer and catalyzer, after the dissolving, hydrogen peroxide (concentration is 30% weight) is added drop-wise to aqueous phase fully.The temperature of polyreaction is 105 ℃, and the time of polyreaction is 9.0 hours.
The number-average molecular weight of the polymer of butene diacid that polyreaction obtains is 1200.
Embodiment 4
Polymerization reactor is identical with embodiment 1 with polymerization process.
The monomer of polyreaction is MALEIC ANHYDRIDE and methyl-maleic acid acid anhydride, and its weight ratio is 1: 1, and catalyzer is a ferric ammonium sulfate, and initiator is hydrochloric acid amidino groups sec.-propyl azo and hydrogen peroxide.
The concentration of monomer in the aqueous solution is 50% weight, and the concentration of catalyzer in the aqueous solution is 300mg/L, and the add-on of initiator hydrochloric acid amidino groups sec.-propyl azo is the 0.5g/mol monomer, and the add-on of initiator hydrogen peroxide is the 18g/mol monomer; Also contain phosphorous acid and Hypophosporous Acid, 50 in the polymerization aqueous phase, its weight ratio is 1: 1, and its total phosphorous is 2.0% of a total monomer weight.
The adding method of initiator is: hydrochloric acid amidino groups sec.-propyl azo is joined (concentration is 30% weight) in the aqueous hydrogen peroxide solution, after the dissolving, be added drop-wise to the aqueous phase that contains monomer and catalyzer together fully.
The temperature of polyreaction is 100 ℃, and the time of polyreaction is 5.5 hours.
The number-average molecular weight of the polymer of butene diacid that polyreaction obtains is 1000.
Embodiment 5
Polymerization reactor is identical with embodiment 1 with polymerization process.
The monomer of polyreaction also comprises vinylformic acid, and the mol ratio of vinylformic acid and MALEIC ANHYDRIDE is 0.05.Other polymeric reaction conditions are identical with embodiment 1.
The number-average molecular weight of the polymer of butene diacid that polyreaction obtains is 975.
Embodiment 6
Polymerization reactor is identical with embodiment 1 with polymerization process.
The monomer of polyreaction also comprises propenyl sulfonic acid, and the mol ratio of propenyl sulfonic acid and MALEIC ANHYDRIDE is 0.1.Other polymeric reaction conditions are identical with embodiment 1.
The number-average molecular weight of the polymer of butene diacid that polyreaction obtains is 950.
Embodiment 7
Polymerization reactor is identical with embodiment 1 with polymerization process.
The monomer of polyreaction also comprises acrylamide, and the mol ratio of acrylamide and MALEIC ANHYDRIDE is 0.2.Other polymeric reaction conditions are identical with embodiment 1.
The number-average molecular weight of the polymer of butene diacid that polyreaction obtains is 990.
Embodiment 8
Polymerization reactor is identical with embodiment 1 with polymerization process.
The monomer of polyreaction is that methyl-maleic acid acid anhydride, catalyzer are that copper sulfate, initiator are hydrochloric acid amidino groups sec.-propyl azo and hydrogen peroxide.
The concentration of monomer in the aqueous solution is 40% weight, and the concentration of catalyzer in the aqueous solution is 200mg/L, and the add-on of initiator hydrochloric acid amidino groups sec.-propyl azo is the 0.1g/mol monomer, and the add-on of initiator hydrogen peroxide is the 9g/mol monomer.
The adding method of initiator is: hydrochloric acid amidino groups sec.-propyl azo is joined (concentration is 30% weight) in the aqueous hydrogen peroxide solution, after the dissolving, be added drop-wise to the aqueous phase that contains monomer and catalyzer together fully.
The temperature of polyreaction is 60 ℃, and the time of polyreaction is 3.0 hours.
The number-average molecular weight of the polymer of butene diacid that polyreaction obtains is 808.
Comparative Examples 1
Polymerization reactor is identical with embodiment 1 with polymerization process.
Initiator is a hydrogen peroxide, and its add-on is 30g/mol monomer (not using hydrochloric acid amidino groups sec.-propyl azo as initiator).Other polymeric reaction conditions are identical with embodiment 1.
The number-average molecular weight of the polymer of butene diacid that polyreaction obtains is 690, and the molecular weight distribution coefficient is 3.06.
Polymerization equipment, reaction mass, reaction process and the reaction conditions of embodiment 1 and Comparative Examples 1 are identical, add hydrochloric acid amidino groups sec.-propyl azo among the embodiment 1 as initiator, the number-average molecular weight of the polymer of butene diacid that obtains improves, molecular weight distribution is concentrated, thereby has improved the quality product as the polymer of butene diacid of water conditioner.
Claims (11)
1, a kind of preparation method of polymer of butene diacid, this method comprises:
Polyreaction is carried out at aqueous phase; Described aqueous phase contains monomer and catalyzer, and initiator is joined this aqueous phase, carries out polyreaction;
Described monomer comprises one or more in butene dioic acid and the derivative thereof, and described derivative is maleic acid anhydride and butene dioic acid salt; Described catalyzer is one or more of transition metal salt; Described initiator is the mixture of hydrochloric acid amidino groups sec.-propyl azo and hydrogen peroxide;
The concentration of described monomer in the aqueous solution is 10～60% weight; The concentration of described catalyzer in the aqueous solution is 100～500mg/l; The add-on of described initiator hydrochloric acid amidino groups sec.-propyl azo is: greater than the 0g/mol monomer, smaller or equal to the 10g/mol monomer; The add-on of described initiator hydrogen peroxide is 9～60g/mol monomer;
The temperature of polyreaction is 60～105 ℃; The time of polyreaction is 3.0～9.0 hours.
2, the preparation method of a kind of polymer of butene diacid according to claim 1 is characterized in that:
Described monomer is selected from: one or more in maleic acid, MALEIC ANHYDRIDE, methyl-maleic acid acid anhydride, the FUMARIC ACID TECH GRADE.
3, the preparation method of a kind of polymer of butene diacid according to claim 1 is characterized in that:
Described catalyzer is selected from: one or more in the water-soluble salt of iron, copper.
4, the preparation method of a kind of polymer of butene diacid according to claim 1 is characterized in that:
The concentration of described monomer in the aqueous solution is 40～50% weight.
5, the preparation method of a kind of polymer of butene diacid according to claim 1 is characterized in that:
The concentration of described catalyzer in the aqueous solution is 200～300mg/l.
6, the preparation method of a kind of polymer of butene diacid according to claim 1 is characterized in that:
The add-on of described initiator hydrochloric acid amidino groups sec.-propyl azo is 0.1～1.0g/mol monomer;
The add-on of described initiator hydrogen peroxide is 18～30g/mol monomer.
7, the preparation method of a kind of polymer of butene diacid according to claim 1 is characterized in that:
The temperature of described polyreaction is 90～105 ℃;
The time of described polyreaction is 3.0～6.0 hours.
8, the preparation method of a kind of polymer of butene diacid according to claim 1 is characterized in that:
Described monomer comprises: one or more in unsaturated carboxylic acid monomer, unsaturated " non-carboxylic " acid mono and the unsaturated non-acid mono beyond the butene dioic acid; In polymerization aqueous phase, the mol ratio of above-mentioned monomer total amount and butene dioic acid and derivatives monomer total amount thereof is: greater than 0, smaller or equal to 0.2.
9, the preparation method of a kind of polymer of butene diacid according to claim 8 is characterized in that:
Described unsaturated carboxylic acid monomer is selected from: one or more in vinylformic acid, methacrylic acid, the hydroxyl acrylic;
Described unsaturated " non-carboxylic " acid mono is selected from: one or more in allyl sulphonic acid, allyl group phosphonic acids, the allyl group oxygen Phenylsulfonic acid;
Described unsaturated non-acid mono is selected from: one or more in acrylamide, N tert butyl acrylamide, the N-vinyl pyrrolidone.
10, according to the preparation method of the described a kind of polymer of butene diacid of one of claim 1～9, it is characterized in that:
Contain in Hypophosporous Acid, 50, phosphorous acid, hypophosphite and the phosphite one or more in the polymerization aqueous phase, its phosphorus content is 0.1～10% of a total monomer weight.
11, the preparation method of a kind of polymer of butene diacid according to claim 10 is characterized in that:
Described phosphorus content is 0.5～2.0% of a total monomer weight.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109721813A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | Polypropylene modification composition and modified polypropene |
| CN109970914A (en) * | 2017-12-28 | 2019-07-05 | 中国石油天然气股份有限公司 | A kind of starch base antisludging agent and its preparation method and application |
| WO2021088455A1 (en) * | 2019-11-08 | 2021-05-14 | 山东泰和水处理科技股份有限公司 | Method for synthesizing hydrolyzed polymaleic anhydride |
| CN115608410A (en) * | 2021-07-13 | 2023-01-17 | 中国石油化工股份有限公司 | Catalyst for synthesizing n-butyl acetate and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1037366A (en) * | 1988-03-14 | 1989-11-22 | 南京师范大学 | Self-stripping metallic rust remover |
| US5055540A (en) * | 1990-02-06 | 1991-10-08 | Rohm And Haas Company | Process for efficient molecular weight control in copolymerization |
| CN1035437C (en) * | 1993-12-21 | 1997-07-16 | 中国石油化工总公司石油化工科学研究院 | Diesel-oil flow improving agent and its preparation method |
| FR2761366A1 (en) * | 1997-03-26 | 1998-10-02 | Synthron | Amphoteric graft copolymers useful as dispersants |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109721813A (en) * | 2017-10-27 | 2019-05-07 | 中国石油化工股份有限公司 | Polypropylene modification composition and modified polypropene |
| CN109721813B (en) * | 2017-10-27 | 2021-09-21 | 中国石油化工股份有限公司 | Polypropylene modified composition and modified polypropylene |
| CN109970914A (en) * | 2017-12-28 | 2019-07-05 | 中国石油天然气股份有限公司 | A kind of starch base antisludging agent and its preparation method and application |
| WO2021088455A1 (en) * | 2019-11-08 | 2021-05-14 | 山东泰和水处理科技股份有限公司 | Method for synthesizing hydrolyzed polymaleic anhydride |
| CN115608410A (en) * | 2021-07-13 | 2023-01-17 | 中国石油化工股份有限公司 | Catalyst for synthesizing n-butyl acetate and preparation method and application thereof |
| CN115608410B (en) * | 2021-07-13 | 2023-10-13 | 中国石油化工股份有限公司 | Catalyst for synthesizing n-butyl acetate and preparation method and application thereof |
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