CN100567347C - A kind of siloxanes reunion acryhic material and synthetic technology thereof of containing - Google Patents
A kind of siloxanes reunion acryhic material and synthetic technology thereof of containing Download PDFInfo
- Publication number
- CN100567347C CN100567347C CNB2007100287586A CN200710028758A CN100567347C CN 100567347 C CN100567347 C CN 100567347C CN B2007100287586 A CNB2007100287586 A CN B2007100287586A CN 200710028758 A CN200710028758 A CN 200710028758A CN 100567347 C CN100567347 C CN 100567347C
- Authority
- CN
- China
- Prior art keywords
- siloxanes
- reunion
- synthetic technology
- acrylate
- carbonic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Landscapes
- Silicon Polymers (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The present invention is a kind of siloxanes reunion acryhic material and synthetic technology thereof of containing.This material is vinylformic acid and alkenyl siloxane or the polymkeric substance that contains siloxanes acrylate and esters of acrylic acid.This synthetic technology is to be 0.5～99.5: 0.1～99.5: 0～99.5 in molar ratio in reactor, adds vinylformic acid and alkenyl siloxane successively or contains siloxanes acrylate and acrylate, adds the initiator of total monomer weight 0.01～5.0wt% then; Carbonic acid gas is 8～25MPa to pressure, is warming up to 40～100 ℃ simultaneously, reacts 2～8 hours, and product uses the extracting of carbonic acid gas original position to constant weight.The invention solves the organo-siloxane monomer and can not successfully be grafted to a difficult problem on the main chain, excellent product quality, do not have any pollution, can be widely used in tertiary oil recovery, solar energy converting, water treatment, emulsion paint, soil improvement and the daily necessities that material purity is had relatively high expectations, food, medical.
Description
Technical field
The present invention relates to a kind of technology of preparing of polyelectrolyte, be meant a kind of siloxanes reunion acryhic material and synthetic technology thereof of in supercritical co, containing especially.
Background technology
The water-soluble polymers product is widely used in tertiary oil recovery, solar energy converting, water treatment, emulsion paint, food, soil improvement, film and friction drag reduction and water-borne coatings, printing ink, makeup, papermaking, pharmaceutical preparation or textile printing and dyeing.In order to give water-soluble polymers some properties, often take approach such as copolymerization, crosslinked, association to realize.
Because water-soluble monomer and oil-soluble monomer polarity difference are very big, both immiscible polymerization techniques that makes are very complicated.Micella copolymerization method, conversed phase micro emulsion copolymerization method, the alternative monomeric species of emulsifier-free emulsion polymerization method are many and synthesis step is simple, and shortcoming is the complicacy that the exhibiting high surface promoting agent that adds will increase last handling process.Novel polymerization process anionoid polymerization, atom transfer radical polymerization, the reversible addition one fracture chain transfer method that can synthesize and control molecular structure by Molecular Structure Design.Shortcoming is that operational condition harshness, alternative monomeric species are few.The raw material that polymer chemistry is modified method is easy to get, but have that the reaction system viscosity is big, problem that water-soluble polymers and oil-soluble monomer are difficult for mixing.
Along with attention and the enhancing of people environmental consciousness and the aggravation of Energy resources crisis of countries in the world to environment protection, it is one of developing direction that the preparation technology of employing green economy prepares environment amenable high-performance polymer.
The synthetic method of multipolymer is normally carried out in aqueous solvent, organic solvent or their mixture.With an organic solvent its toxicity and inflammableness are made troubles to operation, and product also will be polluted, and constitute adverse influence for the application in fields such as daily necessities, food, and the last handling process of product is cumbersome.In addition, siloxanyl monomers solubleness in water is low, can not make water-soluble monomer and oil soluble thorough mixing even, and because the hydrolysis and the condensation reaction of siloxanes easily take place siloxanyl monomers.This is reflected in the water solvent and competes with the addition reaction formation of alkenyl-functional groups, and addition reaction is very slower than hydrolysis-condensation reaction, causes the organo-siloxane monomer successfully not to be grafted on the main chain.When with an organic solvent being medium, because the dissolubility difference of water-soluble monomer and oil-soluble monomer, make that each monomeric amount can not reach arbitrary proportion in the prepared polymkeric substance, end-use is limited for this reason.
Normally polymerization in the aqueous solution of acrylate copolymer commercial production, in order to obtain commodity polyacrylic acid solid, at high temperature dewatered drying has consumed a large amount of energy.And the suspension in organic solvent, dispersion, precipitation polymerization, reaction needs to carry out separating of product and solvent after finishing, and is one and has not only consumed energy but also time-consuming process.And solvent toxicity and inflammableness make troubles to operation, and the volatilization of various organic solvents and discharging have caused serious pollution to environment, and product also will be polluted.
Summary of the invention
The objective of the invention is to overcome the above-mentioned shortcoming of prior art, solution organo-siloxane monomer can not successfully be grafted to the gordian technique on the main chain, and a kind of siloxanes reunion acryhic material and synthetic technology thereof of containing in supercritical co is provided.
The siloxanes reunion acryhic material that contains of the present invention is vinylformic acid and alkenyl siloxane or the polymkeric substance that contains siloxanes acrylate and esters of acrylic acid, and its structural formula is as follows:
In the structural formula of multipolymer, X is a water-soluble monomer vinylformic acid, and its mol ratio is 0.5～99.5; Y is the siloxane groups monomer, and its mol ratio is 0.1～99.5; Z is an acrylic ester monomer, and its mol ratio is 0～99.5; R
1=H or CH
3, R
2=Si (OCH
3)
1-3, Si (OCH
2CH
3)
1-3Or COO (CH
2)
3Si (OCH
3)
1-3, R
3=(CH
2) nCH
3, n=4～36.
The synthetic technology that contains siloxanes reunion acryhic material in supercritical co that the present invention proposes is characterized in that reaction medium is a supercritical co, and its step and processing condition are as follows:
Step 1:
In reactor, add vinylformic acid, alkenyl siloxane or contain siloxanes acrylate, acrylate, wherein vinylformic acid, vinylsiloxane or the mol ratio that contains siloxanes acrylate, acrylate are 0.5～99.5: 0.1～99.5: 0～99.5, add the initiator of total monomer weight 0.01～5.0wt% then;
Step 2:
After feeding the amounts of carbon dioxide exhausted air earlier, squeezing into carbonic acid gas with high-pressure metering pump again is 8～25Mpa to pressure, closes intake valve; Start magnetic stirring apparatus, progressively be warming up to 40～100 ℃ simultaneously, reacted 2～8 hours, reaction finishes the postcooling reactor, slowly emits carbonic acid gas again, the white powder product that obtains loosening;
Step 3:
With the extracting of carbonic acid gas original position, temperature is 30～60 ℃ to the synthetic product in autoclave, and pressure is 8～16MPa, and repeatedly extracting is up to the product constant weight, and the white powder that is obtained promptly contains the polyacrylic acid material of siloxanes group.
The above-mentioned synthetic technology that contains the polyacrylic acid material of siloxanes group, the total monomer weight that adds reactor is the best with 0.1～0.5kg/L.
Described best polymeric reaction temperature is that 50～80 ℃, polymerization pressure are 12～20Mpa, polymerization reaction time 3～6 hours.
Described initiator is meant azo-compound or superoxide or persulphate or oxidation-reduction system class initiator; Can be preferably from Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), dibenzoyl peroxide, peroxidation two acyls, Potassium Persulphate, ammonium persulphate.
Of the present invention contain siloxanes reunion acryhic material water-soluble in following reaction takes place: the hydrolysis reaction of (1) active organosilicon oxygen alkane, the hydrolysis of hydrophobic monomer siloxanes generates silanol and small molecular alcohol.(2) condensation reaction then taking place, produces the Si-O-Si chemically crosslinked between the silanol and between siloxanes and the silanol.The hydrolysis and the condensation reaction of siloxanes generation siloxanes, the dynamic physical cross-linked network synergy that chemically crosslinked network that self-crosslinking produces and siloxane groups generation association are produced increases hydrodynamic volume, and soltion viscosity obviously raises.The hydrophobic association effect takes place in esters of acrylic acid in water, hydrodynamic volume is increased, and soltion viscosity obviously raises.
The present invention compares with above-mentioned prior art has following advantage:
1, the present invention with free of contamination supercritical co as an alternative solvent in the application in Polymer Synthesizing field, successful solution the organo-siloxane monomer can not successfully be grafted to a difficult problem on the main chain, the carbonic acid gas wide material sources, environmental sound, inertia is conducted heat, rate of mass transfer is fast, the easily separated purifying of product.Alkenyl siloxane monomer, esters of acrylic acid and vinylformic acid can effectively protect siloxane groups not participate in reaction by carry out copolyreaction in supercritical co, can prepare the organic siloxane modified acrylic copolymer of novel self-cross linking type.
2, with the extracting of carbonic acid gas original position, repeatedly extracting is up to the product constant weight in autoclave for the synthetic product, and unreacted monomer can both be dissolved in the supercritical co, and multipolymer is then insoluble, therefore can reach the purifying requirement.
3, in the prepared polymer architecture of the present invention, each monomeric amount can reach arbitrary proportion in the polymkeric substance, and siloxane groups do not participate in reaction in supercritical co, can further participate in reaction when polymer application.
4, solvent for use supercritical co of the present invention is because cheap, and nontoxic pollution-free is nonflammable explosive, is convenient to reclaim; The simple environmental protection of synthetic method, with the medium of supercritical co as polyreaction, polyreaction is easy to control.Last in addition product does not have any pollution, is the exsiccant white powder, is convenient to transportation.
5, the prepared product of the present invention is a kind of good multipolymer, as polyelectrolyte, to the pH sensitivity; As the modified soluble complex polyelectrolyte particle, can improve it by tensio-active agent again and form and effect.It is the novel polyelectrolyte that contains siloxanes group of a class likely.Can be widely used in tertiary oil recovery, solar energy converting, water treatment, emulsion paint, soil improvement, film and friction drag reduction and water-borne coatings, printing ink, makeup, papermaking or textile printing and dyeing, be particularly suitable for application the higher daily necessities of the purity requirement of material, food, field such as medical.
Description of drawings
Fig. 1 is the polymer concentration and the viscosity relationship curve of embodiment of the present invention 1;
Fig. 2 is the polymer viscosity and the shearing rate relation curve of embodiment of the present invention 2;
Fig. 3 is the polymer viscosity and the pH relation curve of embodiment of the present invention 3.
Embodiment
Below in conjunction with embodiment the present invention is further detailed, present embodiment is to concrete detailed description of the present invention, content of the present invention is not made any restriction.
The synthetic technology that in supercritical co, contains siloxanes reunion acryhic material that the present invention proposes, raw material propylene acid (AA) is analytical pure, stopper is removed in underpressure distillation; Initiator is Diisopropyl azodicarboxylate (AIBN), uses recrystallizing methanol; Siloxanyl monomers vinyltriethoxysilane (military big organosilicon company) does not deal with.
Synthetic technology step and processing condition are as follows:
Step 1:
Weighing vinylformic acid 2.1g, vinyltriethoxysilane 0.05g, butyl acrylate 0.25g, Diisopropyl azodicarboxylate 0.021g join in the 20mL stainless steel autoclave and seal;
Step 2:
Feed earlier carbonic acid gas to the 5MPa, pause 30S, slowly air in the still is discharged in venting, repeats 2 times～3 times; Squeezing into carbonic acid gas with high-pressure metering pump again is 16MPa to pressure, closes intake valve; Start magnetic stirring apparatus, progressively be warming up to 60 ℃ simultaneously, reacted 4 hours, reaction finishes the postcooling reactor, slowly emits carbonic acid gas again, the white powder product that obtains loosening;
Step 3:
With the extracting of carbonic acid gas original position, repeatedly extracting is up to the product constant weight in autoclave for the synthetic product, removes in the system unreacted monomer etc. simultaneously.Operational condition: 45 ℃, 15MPa, CO
2Flow 5L/min, extracting time 5min.The cooling reactor is to room temperature, and final product is collected in slowly venting.The white powder that is obtained is the polyacrylic acid material that contains siloxanes group that meets structural formula of the present invention.Polymkeric substance transformation efficiency 91%, polymkeric substance viscosity-average molecular weight 6.2 * 10
5
It is soluble in water to get polymeric articles, is mixed with different concns solution, and the gained strength of solution records on rotational viscosimeter the influence of viscosity, polymer concentration and viscosity relationship curve are as shown in Figure 1, Fig. 1 shows that the content of siloxanes is lower in the polymkeric substance, can water-solublely play viscosifying action.Can be used for oil tertiary oil recovery, water treatment, emulsion paint textile printing and dyeing.
Embodiment 2
Raw material propylene acid (AA) is analytical pure, and stopper is removed in underpressure distillation; Initiator is Diisopropyl azodicarboxylate (AIBN), uses recrystallizing methanol; Octadecyl acrylate does not deal with available from Aldrich company; Siloxanyl monomers vinyltriethoxysilane (military big organosilicon company) does not deal with;
Synthetic technology step and processing condition are as follows:
Step 1:
Weighing vinylformic acid 2.1g, the different dibutyronitrile 0.021g of azo, octadecyl acrylate 0.2333g, vinyltriethoxysilane 0.04g join in the 20mL stainless steel autoclave and seal;
Step 2:
Feed earlier carbonic acid gas to the 6MPa, pause 10S, slowly air in the still is discharged in venting, repeats 2 times～3 times; Squeezing into carbonic acid gas with high-pressure metering pump again is 14MPa to pressure, closes intake valve; Start magnetic stirring apparatus, progressively be warming up to 65 ℃ simultaneously, reacted 5 hours, reaction finishes the postcooling reactor, slowly emits carbonic acid gas again, the white powder product that obtains loosening;
Step 3:
With the extracting of carbonic acid gas original position, repeatedly extracting is up to the product constant weight in autoclave for the synthetic product, removes in the system unreacted monomer etc. simultaneously.Operational condition: 55 ℃, 14MPa, CO
2Flow 5L/min, extracting time 3min.The cooling reactor is to room temperature, and final product is collected in slowly venting.The white powder that is obtained is the polyacrylic acid material that contains siloxanes group that meets structural formula of the present invention.Polymkeric substance transformation efficiency 92%, polymkeric substance viscosity-average molecular weight 7.2 * 10
5
It is soluble in water to get polymeric articles, be mixed with different concns solution, gained solution shear speed records on rotational viscosimeter the influence of viscosity, and polymer viscosity and shearing rate relation curve are as shown in Figure 2, Fig. 2 shows that its rheological property can be used as water-borne coatings, printing ink, makeup.
Embodiment 3
Raw material propylene acid (AA) is analytical pure, and stopper is removed in underpressure distillation; Initiator is a 2,2'-Azobis(2,4-dimethylvaleronitrile), uses recrystallizing methanol; Siloxanyl monomers vinyl hexyl Trimethoxy silane, vinylformic acid three hexadecyl esters do not deal with available from Aldrich company;
Synthetic technology step and processing condition are as follows:
Step 1:
Weighing vinylformic acid 2.0g, 2,2'-Azobis(2,4-dimethylvaleronitrile) 0.021g, vinylformic acid three hexadecyl ester 0.2333g, vinyl hexyl Trimethoxy silane 0.05g join in the 20mL stainless steel autoclave and seal;
Step 2:
Feed earlier carbonic acid gas to the 6MPa, pause 20S, slowly air in the still is discharged in venting, repeats 2 times～3 times; Squeezing into carbonic acid gas with high-pressure metering pump again is 15MPa to pressure, closes intake valve; Start magnetic stirring apparatus, progressively be warming up to 60 ℃ simultaneously, reacted 6 hours, reaction finishes the postcooling reactor, slowly emits carbonic acid gas again, the white powder product that obtains loosening;
Step 3:
With the extracting of carbonic acid gas original position, repeatedly extracting is up to the product constant weight in autoclave for the synthetic product, removes in the system unreacted monomer etc. simultaneously.Operational condition: 40 ℃, 12MPa, CO
2Flow 5L/min, extracting time 1min.The cooling reactor is to room temperature, and final product is collected in slowly venting.The white powder that is obtained is the polyacrylic acid material that contains siloxanes group that meets structural formula of the present invention.Polymkeric substance transformation efficiency 91%, polymkeric substance viscosity-average molecular weight 8.2 * 10
5
The pH susceptibility of prepared solution records polymer viscosity and pH relation curve as shown in Figure 3 on rotational viscosimeter, Fig. 3 shows that its pH triggered response performance useful as drug slowly-releasing also can be used for papermaking or textile printing and dyeing.
Raw material propylene acid (AA) is analytical pure, and stopper is removed in underpressure distillation; Initiator is a dibenzoyl peroxide; Process Conditions of Cetane Acrylate, Tianjin chemical reagent company limited; Siloxanyl monomers is Y-methacryloxypropyl trimethoxy silane (a military big organosilicon company), does not deal with;
Synthetic technology step and processing condition are as follows:
Step 1:
Weighing vinylformic acid 0.15g, dibenzoyl peroxide 0.022g, Process Conditions of Cetane Acrylate 0.0779g, Y-methacryloxypropyl trimethoxy silane 2.06g join in the reactor and seal;
Step 2:
Feed earlier carbonic acid gas to the 4MPa, pause 3S, slowly air in the still is discharged in venting, repeats 2 times～3 times; Squeezing into carbonic acid gas with high-pressure metering pump again is 8MPa to pressure, closes intake valve; Start magnetic stirring apparatus, progressively be warming up to 75 ℃ simultaneously, reacted 8 hours, reaction finishes the postcooling reactor, slowly emits carbonic acid gas again, the white powder product that obtains loosening;
Step 3:
With the extracting of carbonic acid gas original position, repeatedly extracting is up to the product constant weight in autoclave for the synthetic product, removes in the system unreacted monomer etc. simultaneously.Operational condition: 45 ℃, 12MPa, CO
2Flow 2L/min, extracting time 1min.The cooling reactor is to room temperature, and final product is collected in slowly venting.The white powder that is obtained is the polyacrylic acid material that contains siloxanes group that meets structural formula of the present invention.Polymkeric substance transformation efficiency 92%, polymkeric substance viscosity-average molecular weight 5.8 * 10
5Can be used for food, soil improvement, film and friction drag reduction.
Embodiment 5
Raw material propylene acid (AA) is analytical pure, and stopper is removed in underpressure distillation; Initiator is peroxidation two acyls, uses recrystallizing methanol; Dodecyl acrylate, Tianjin chemical reagent company limited; Siloxanyl monomers is a vinyltrimethoxy silane, and (military big organosilicon company) do not deal with;
Synthetic technology step and processing condition are as follows:
Step 1:
Weighing vinylformic acid 1.9g, peroxidation two acyl 0.011g, dodecyl acrylate 0.0834g, vinyltrimethoxy silane 0.15g join in the reactor and seal;
Step 2:
Feed earlier carbonic acid gas to the 8MPa, pause 2S, slowly air in the still is discharged in venting, repeats 2 times～3 times; Squeezing into carbonic acid gas with high-pressure metering pump again is 25MPa to pressure, closes intake valve; Start magnetic stirring apparatus, progressively be warming up to 50 ℃ simultaneously, reacted 4 hours, reaction finishes the postcooling reactor, slowly emits carbonic acid gas again, the white powder product that obtains loosening;
Step 3:
With the extracting of carbonic acid gas original position, repeatedly extracting is up to the product constant weight in autoclave for the synthetic product, removes in the system unreacted monomer etc. simultaneously.Operational condition: 35 ℃, 9MPa, CO
2Flow 2L/min, extracting time 2min.The cooling reactor is to room temperature, and final product is collected in slowly venting.The white powder that is obtained is the polyacrylic acid material that contains siloxanes group that meets structural formula of the present invention.Polymkeric substance transformation efficiency 91%, polymkeric substance viscosity-average molecular weight 6.8 * 10
5Can be used for oil tertiary oil recovery, water treatment, emulsion paint textile printing and dyeing.
Raw material propylene acid (AA) is analytical pure, and stopper is removed in underpressure distillation; Initiator is Diisopropyl azodicarboxylate (AIBN), uses recrystallizing methanol; Butyl acrylate, Tianjin chemical reagent company limited; Siloxanyl monomers is methyl ethylene diethoxy silane (a military big organosilicon company), does not deal with;
Synthetic technology step and processing condition are as follows:
Step 1:
Weighing vinylformic acid 1.1g, Diisopropyl azodicarboxylate 0.1g, butyl acrylate 0.1356g, methyl ethylene diethoxy silane 1.07g join in the reactor and seal;
Step 2:
Feed earlier carbonic acid gas to the 6MPa, pause 2S, slowly air in the still is discharged in venting, repeats 2 times～3 times; Squeezing into carbonic acid gas with high-pressure metering pump again is 25MPa to pressure, closes intake valve; Start magnetic stirring apparatus, progressively be warming up to 40 ℃ simultaneously, reacted 8 hours, reaction finishes the postcooling reactor, slowly emits carbonic acid gas again, the white powder product that obtains loosening;
Step 3:
With the extracting of carbonic acid gas original position, repeatedly extracting is up to the product constant weight in autoclave for the synthetic product, removes in the system unreacted monomer etc. simultaneously.Operational condition: 35 ℃, 9MPa, CO
2Flow 2L/min, extracting time 2min.The cooling reactor is to room temperature, and final product is collected in slowly venting.The white powder that is obtained is the polyacrylic acid material that contains siloxanes group that meets structural formula of the present invention.Polymkeric substance transformation efficiency 89%, polymkeric substance viscosity-average molecular weight 6.9 * 10
5Can be used for food, soil improvement, film and friction drag reduction.
Embodiment 7
Raw material propylene acid (AA) is analytical pure, and stopper is removed in underpressure distillation; Initiator is a 2,2'-Azobis(2,4-dimethylvaleronitrile), uses recrystallizing methanol; Siloxanyl monomers is vinyltriethoxysilane (a military big organosilicon company), does not deal with;
Synthetic technology step and processing condition are as follows:
Step 1:
Weighing vinylformic acid 1.7g, 2,2'-Azobis(2,4-dimethylvaleronitrile) 0.022g, vinyltriethoxysilane 0.58g join in the reactor and seal.
Step 2:
Feed earlier carbonic acid gas to the 5MPa, pause 50S, slowly air in the still is discharged in venting, repeats 2 times～3 times; Squeezing into carbonic acid gas with high-pressure metering pump again is 9MPa to pressure, closes intake valve; Start magnetic stirring apparatus, progressively be warming up to 100 ℃ simultaneously, reacted 3 hours, reaction finishes the postcooling reactor, slowly emits carbonic acid gas again, the white powder product that obtains loosening;
Step 3:
With the extracting of carbonic acid gas original position, repeatedly extracting is up to the product constant weight in autoclave for the synthetic product, removes in the system unreacted monomer etc. simultaneously.Operational condition: 40 ℃, 12MPa, CO
2Flow 5L/min, extracting time 1min.The cooling reactor is to room temperature, and final product is collected in slowly venting.The white powder that is obtained is the polyacrylic acid material that contains siloxanes group that meets structural formula of the present invention.Polymkeric substance transformation efficiency 90%, polymkeric substance viscosity-average molecular weight 7.2 * 10
5Can be used for water-borne coatings, printing ink, makeup.
Embodiment 8
Raw material propylene acid (AA) is analytical pure, and stopper is removed in underpressure distillation; Initiator is a Potassium Persulphate; Siloxanyl monomers is that vinyl three (β methoxy ethoxy) silane (military big organosilicon company) does not deal with;
Synthetic technology step and processing condition are as follows:
Step 1:
Weighing vinylformic acid 1.5g, Potassium Persulphate 0.022g, vinyl three (β methoxy ethoxy) silane 0.39g join in the reactor and seal;
Step 2:
Feed earlier carbonic acid gas to the 6MPa, pause 10S, slowly air in the still is discharged in venting, repeats 2 times～3 times; Squeezing into carbonic acid gas with high-pressure metering pump again is 20MPa to pressure, closes intake valve; Start magnetic stirring apparatus, progressively be warming up to 80 ℃ simultaneously, reacted 2 hours, reaction finishes the postcooling reactor, slowly emits carbonic acid gas again, the white powder product that obtains loosening;
Step 3:
With the extracting of carbonic acid gas original position, repeatedly extracting is up to the product constant weight in autoclave for the synthetic product, removes in the system unreacted monomer etc. simultaneously.Operational condition: 55 ℃, 14MPa, CO
2Flow 5L/min, extracting time 3min.The cooling reactor is to room temperature, and final product is collected in slowly venting.The white powder that is obtained is the polyacrylic acid material that contains siloxanes group that meets structural formula of the present invention.Polymkeric substance transformation efficiency 89%, polymkeric substance viscosity-average molecular weight 6.2 * 10
5Can be used for papermaking, pharmaceutical preparation or textile printing and dyeing.
Embodiment 9
Raw material propylene acid (AA) is analytical pure, and stopper is removed in underpressure distillation; Initiator is an ammonium persulphate; Siloxanyl monomers is Y-methacryloxypropyl trimethoxy silane (a military big organosilicon company), does not deal with;
Synthetic technology step and processing condition are as follows:
Step 1:
Weighing vinylformic acid 1.0g, ammonium persulphate 0.023g, Y-methacryloxypropyl trimethoxy silane 1.06g join in the reactor and seal;
Step 2:
Feed earlier carbonic acid gas to the 5MPa, pause 5S, slowly air in the still is discharged in venting, repeats 2 times～3 times; Squeezing into carbonic acid gas with high-pressure metering pump again is 14MPa to pressure, closes intake valve; Start magnetic stirring apparatus, progressively be warming up to 50 ℃ simultaneously, reacted 8 hours, reaction finishes the postcooling reactor, slowly emits carbonic acid gas again, the white powder product that obtains loosening;
Step 3:
With the extracting of carbonic acid gas original position, repeatedly extracting is up to the product constant weight in autoclave for the synthetic product, removes in the system unreacted monomer etc. simultaneously.Operational condition: 45 ℃, 15MPa, CO
2Flow 5L/min, extracting time 1min.The cooling reactor is to room temperature, and final product is collected in slowly venting.The white powder that is obtained is the polyacrylic acid material that contains siloxanes group that meets structural formula of the present invention.Polymkeric substance transformation efficiency 92%, polymkeric substance viscosity-average molecular weight 6.5 * 10
5Can be used for water-borne coatings, printing ink, makeup, water treatment.
Claims (6)
1, a kind of synthetic technology that contains siloxanes reunion acryhic material, it is characterized in that: reaction medium is a supercritical co, its step and processing condition are as follows:
Step 1:
In reactor, add vinylformic acid and alkenyl siloxane or contain siloxanes acrylate and acrylate, wherein vinylformic acid, vinylsiloxane or the mol ratio that contains siloxanes acrylate, acrylate are 0.5～99.5: 0.1～99.5: 0～99.5, add the initiator of total monomer weight 0.01～5.0wt% then;
Step 2:
After feeding the amounts of carbon dioxide exhausted air earlier, squeezing into carbonic acid gas with high-pressure metering pump again is 8～25Mpa to pressure, closes intake valve; Start magnetic stirring apparatus, progressively be warming up to 40～100 ℃ simultaneously, reacted 2～8 hours, reaction finishes the postcooling reactor, slowly emits carbonic acid gas again, the white powder product that obtains loosening;
Step 3:
With the extracting of carbonic acid gas original position, temperature is 30～60 ℃ to the synthetic product in autoclave, and pressure is 8～16MPa, and repeatedly extracting is up to the product constant weight, and the white powder that is obtained promptly contains the polyacrylic acid material of siloxanes group.
2, a kind of synthetic technology that contains siloxanes reunion acryhic material according to claim 1, it is characterized in that: the total monomer weight of described adding reactor is 0.1～0.5kg/L.
3, a kind of synthetic technology that contains siloxanes reunion acryhic material according to claim 1 and 2 is characterized in that: described polymeric reaction temperature is that 50～80 ℃, polymerization pressure are 12～20Mpa, polymerization reaction time 3～6 hours.
4, a kind of synthetic technology that contains siloxanes reunion acryhic material according to claim 1 and 2 is characterized in that: described initiator is meant azo-compound or superoxide or persulphate or oxidation-reduction system class initiator.
5, a kind of synthetic technology that contains siloxanes reunion acryhic material according to claim 4, it is characterized in that: described initiator is selected from Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), dibenzoyl peroxide, Potassium Persulphate or ammonium persulphate.
6, the described a kind of synthetic technology preparation that contains siloxanes reunion acryhic material of claim 1～5 contains siloxanes reunion acryhic material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100287586A CN100567347C (en) | 2007-06-22 | 2007-06-22 | A kind of siloxanes reunion acryhic material and synthetic technology thereof of containing |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007100287586A CN100567347C (en) | 2007-06-22 | 2007-06-22 | A kind of siloxanes reunion acryhic material and synthetic technology thereof of containing |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101096394A CN101096394A (en) | 2008-01-02 |
| CN100567347C true CN100567347C (en) | 2009-12-09 |
Family
ID=39010497
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2007100287586A Expired - Fee Related CN100567347C (en) | 2007-06-22 | 2007-06-22 | A kind of siloxanes reunion acryhic material and synthetic technology thereof of containing |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100567347C (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103554514A (en) * | 2013-10-30 | 2014-02-05 | 江苏上田环境修复有限公司 | Chelating agent for recovering heavy metal-contaminated soil, and preparation and usage methods thereof |
| CN105837734A (en) * | 2016-05-09 | 2016-08-10 | 上海惠昌化工厂 | Organosilicone modified acrylic polyester potash, preparation method and application to cancer prevention and treatment |
| CN107200821A (en) * | 2017-04-21 | 2017-09-26 | 苏州博纳化学科技有限公司 | Dispersant of acrylate vinyl siloxane copolymer and preparation method thereof |
| CN107236092B (en) * | 2017-07-20 | 2019-07-16 | 中海石油(中国)有限公司 | One kind containing silicate sturcture monomer and the preparation method and application thereof |
| CN109503783B (en) * | 2018-12-10 | 2021-07-23 | 万华化学集团股份有限公司 | Terminal siloxane modified polyacrylate block copolymer and preparation method thereof |
| CN113045941A (en) * | 2021-03-19 | 2021-06-29 | 河北水熠木丰工程技术有限责任公司 | Bridge guardrail anticorrosive paint and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1594380A (en) * | 2004-07-09 | 2005-03-16 | 中山大学 | Process for preparing silicon acrylic latex |
-
2007
- 2007-06-22 CN CNB2007100287586A patent/CN100567347C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1594380A (en) * | 2004-07-09 | 2005-03-16 | 中山大学 | Process for preparing silicon acrylic latex |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101096394A (en) | 2008-01-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100567347C (en) | A kind of siloxanes reunion acryhic material and synthetic technology thereof of containing | |
| CN101720335A (en) | Composite material granular and preparation method thereof | |
| CN101121771A (en) | Acryloxyalkoxysilicane modified acrylic acid ester polymerization emulsion and its preparation method and application | |
| CN103923248A (en) | Stable methylacryloyl cage type silsesquioxane emulsion with Pickering effect and preparation thereof | |
| CN106554446A (en) | A kind of fast preparation method of multi-functional fluoropolymer microsphere | |
| CN108329417A (en) | Nano-meter SiO_22/ organic-silicon-modified core-shell acrylic-resin emulsion and preparation method | |
| CN104151563B (en) | A kind of golden nanometer particle of parents' polymer self assembles micella cladding with optical Response | |
| CN102936308A (en) | Method for synthesizing vinyl chloride-vinyl acetate copolymer via solution method | |
| CN110194877A (en) | A kind of Nanometer composite hydrogel and its preparation method and application | |
| CN103483601B (en) | Preparation method for polymeric nanometer microsphere | |
| CN110845913A (en) | Reactive water-based color paste and preparation method thereof | |
| CN104744650A (en) | Preparation and application of hybrid copolymer containing POSS (polyhedral oligomeric silsesquioxane) base | |
| CN103382236A (en) | Silicone-acrylate emulsion with high organosilicon content and preparation method thereof | |
| CN115386047A (en) | Polymer for high-temperature-resistant saline-water-based fracturing fluid thickening agent of oil-gas well | |
| CN106279469B (en) | A kind of quick method for preparing clean polymer microballoon | |
| CN102627826B (en) | Gold nanoparticle with core-shell structure and preparation method thereof | |
| CN103113538A (en) | Fluorine-containing large-molecule coupling agent, and preparation method and application thereof | |
| Wang et al. | Kinetics of dispersion polymerization of dimethyl diallyl ammonium chloride and acrylamide | |
| CN112851937B (en) | Preparation method of dispersible polypyrrole copolymer | |
| CN105879913B (en) | A kind of chitosan film catalysis material of loaded metal ion and preparation method thereof | |
| CN1113912C (en) | Copolymers of carboxylic acids and of polyene-unsaturated carboxylic acid derivatives and their use as thickeners or dispersants | |
| EP1802663A2 (en) | Latex particulates with epoxide functional groups | |
| Zhang et al. | Graft copolymerization of 2‐(dimethylamino) ethyl methacrylate onto carboxymethylated cellulose | |
| CN107057046A (en) | Nucleocapsid hybrid copolymers POSS (PDMAEMA b PDLA)8And its synthetic method and application | |
| CN100567345C (en) | A kind of method of preparing polymer nano micelle by water solution polymerization self-emulsification |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20091209 Termination date: 20130622 |