CN1421466A - Controllable free radical polymerization process with thioether compound as chain transferring agent - Google Patents
Controllable free radical polymerization process with thioether compound as chain transferring agent Download PDFInfo
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- CN1421466A CN1421466A CN 01132381 CN01132381A CN1421466A CN 1421466 A CN1421466 A CN 1421466A CN 01132381 CN01132381 CN 01132381 CN 01132381 A CN01132381 A CN 01132381A CN 1421466 A CN1421466 A CN 1421466A
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Abstract
The controllable free radical polymerization process with thioether compound as chain transferring agent is suitable for producing polymer with polydispersive narrow molecular weight distribution, predictable structure and predictable molecular weight. Under reaction condition, the thioether compound as chain transferring agent is well compatible with serial monomers. The polymerization process prepares polymer with the general expression of Z-(-S-(M)-mR)q in the presence of chain transferring agent of general expression of Z-(S-R)q. The controllable polydispersivity of the polymer varies with the molar proportion of monomer, chain transferring agent and free radical source. The process of the present invention is used to produce polymer for adhesive and paint.
Description
Technical field
The present invention relates to controllable free radical polymerization process, relate to the controllable free radical polymerization process of thioether compound as chain transferring agent or rather.
Background technology
Want to prepare the polymkeric substance of foreseeable polymer architecture and molecular weight in the controllable free-radical polymerisation process, and prepare narrow polydispersion, give the polymkeric substance of polymer terminal group functionality, the selection chain-transfer agent is crucial.The sulfide chain-transfer agent can be given activity to radical polymerization, also novel terminal functionality can be incorporated in the polymkeric substance simultaneously, at prior art (macromoleacles, 1993, [26], 2240) in, a kind of tert-butyl acrylate is disclosed in the presence of two (4-aminophenyl) disulfide, make α through free radical adjustment reaction. the method for ω-diamino functionalized poly (tert-butyl acrylate), the characteristics of this method are tert-butyl acrylates, two (4-aminophenyl) disulfides and azo isobutyronitrile (AIBN) add in the reactor simultaneously, and 25 ℃ of reactions of what prepare polymkeric substance.The molecular weight distribution that obtains is 2.2-2.3, and the polymer terminal group functionality is 0.61-2.5, from experimental result, the molecular weight distribution broad, polymer terminal group functionality from 0.61 to 2.5, data are disperseed, desirable not enough aspect controllable polymerization thus, remaining what further improves.
Summary of the invention
The objective of the invention is chain-transfer agent by choosing, explore feed way and correlated response parameter as charge temperature and reinforced time, temperature of reaction and reaction times etc., prepare narrow polydispersion polymkeric substance with the controlled radical polymerization method, the dispersity that makes polymkeric substance is 1.31-1.69, and functionality is 2.
The present invention carries out controllable free-radical polymerisation with thioether compound as chain transferring agent and prepares the polymkeric substance that the polymer repeat unit structure has general formula (A).
In the formula:
Z is a deutero-m valency residue from many groups that the aryl of any replacement is formed;
M be from
Select arbitrarily in the polymer repeat unit structure of maleic anhydride, N-methyl maleimide, N-aryl maleimide, dialkyl fumarate and cyclic polymer conversion of monomer;
R is the alkyl from any replacement, saturated, unsaturated aromatic carbocyclic or heterocyclic ring, and alkyl sulfide, alkoxyl group, dialkyl amido is selected arbitrarily in the group that organo-metallic class and polymer chain are formed;
U is the C that replaces from oxygen, halogen
1-C
4Select arbitrarily in alkyl, hydroxyl, alkoxyl group, carboxyl, acyloxy, alcoxyl carboxylic an aromatic plant metioned in ancient books, the carboxylic acid ester groups;
V is from hydrogen, R ', COOH, COOR, COR ", CN, CONH
2, CONHR " and halogen in select arbitrarily.
Q is 〉=2 integer
M is 〉=1 integer
R ' chooses any one kind of them the group formed of alkyl, aryl from any replacement and polymer chain;
R " be C from any replacement
1-C
18Alkyl, C
2-C
18Choose any one kind of them in alkane thiazolinyl, aryl, heterocyclic radical, aralkyl, the alkaryl, the substituting group on the alkaryl can be separately from epoxy, hydroxyl; alkoxyl group; acyl group, acyl-oxygen, carbonic acid and carbonate; sulfonic acid and sulfonate; alcoxyl or fragrant oxygen-carbonyl, isocyanate group, itrile group; silyl is chosen any one kind of them in halogen and the dialkyl amido.
General formula (A) polymkeric substance by:
(i) be CH from structure
2The vinyl monomer of=CUV, maleic anhydride, N-alkyl maleic anhydride, N-aryl maleic anhydride, choosing any one kind of them in dialkyl fumarate and the ring-type comonomer has the monomer of repeated structural unit M.
(ii) has general formula (C)
Chain-transfer agent, should (C) formula in R be the free radical activity group, S is that sulphur atom and the radical source that (iii) produces free radical are in contact with one another prepared in reaction.
The M repeat unit structure of general formula (A) is by the vinyl monomer in (I)
Be transformed.
By changing (i), (ii) and the polydispersity of molar ratio controlling polymers (iii).The attribute of polymer repeat unit structure M of the present invention and repeating unit numerical value m decision polymkeric substance.When m 〉=1, when M was single monomer segment, polymkeric substance was a homopolymer; When m 〉=2, be the segment from 2 or a plurality of different monomers, selected when forming at the M of irregular sequence, then polymkeric substance is a multipolymer.When m 〉=2 and M choose any one kind of them from 2 or more a plurality of different monomers segment, its each different monomer segment or monomeric groups appear at discrete sequence, and then polymkeric substance is a segmented copolymer.
General formula (C) thioether chain-transfer agent is from diphenyl sulfide in the present invention, and the benzyl phenyl thioether is chosen any one kind of them in two (phenyl thioether methyl) benzene.
The polymkeric substance of the inventive method preparation can be a random copolymers, segmented copolymer, graft copolymer, any one in star copolymer and the ladder type multipolymer.The terminal functionality of the polymkeric substance of the inventive method preparation is 2.
40-160 ℃ of the inventive method what is added to vinyl monomer and radical source in the chain-transfer agent, and reinforced time remaining 5-15 hour, most examples were 6-8 hour, and the reinforced back what that finishes was kept 2-3 hour for 80-90 ℃, and obtaining monomer conversion is 95%.The polymer dispersed degree is 1.31-1.69, and terminal functionality is 2 polymkeric substance.Better temperature when here, vinyl monomer and radical source are added to chain-transfer agent is 80 ℃.The radical source add-on is 10% of a monomer mixture total amount, is the 0.001-5% weight part preferably.
The inventive method has many advantages compared with the prior art really, and many useful effects are arranged.At first, to prepare the Narrow Polydispersity of narrow polydispersion polymkeric substance be 1.2-2 in the present invention.And monomer conversion is under the situation of 10%-100%, and Narrow Polydispersity remains unchanged.Yet when prior art was 0.1-10% when monomer conversion, corresponding polydispersity was 1.5-2.0, and the polydispersity of correspondence was 2-10 when monomer conversion was 10-100%.The polymer terminal group functionality of the inventive method preparation is 2, and prior art is 0.61-2.5.
The present invention can letex polymerization, and the solution successive polymerization is finished, and reaction is controlled metering reaction, can prepare the polymkeric substance of expection molecular weight and distribution.Can produce the like grafting of polymkeric substance of complex construction, the polymkeric substance of star-like and disproportionation; Can produce aqueous polymers, or solvent is solvable or the dispersive polymkeric substance.
Embodiment
As follows in order to implement the present invention better especially exemplified by going out example, but it is not a limitation of the present invention.
Example 1
0.06g the solution of benzyl phenyl thioether in 4ml toluene is heated to 80 ℃, in 12 hours, add azo isobutyronitrile (AIBN) and vinylbenzene (0.0031g is in 2ml vinylbenzene) continuously, reaction mixture during certain in sampling analysis, after monomer has added, the temperature of reaction what was kept 3 hours for 90 ℃, last monomer conversion is up to 95%, and detailed the results are shown in Table 1.
The relation in table 1 polystyrene molecular weight and reaction times
| Project | Time/h | Number-average molecular weight Mn | Molecular weight distribution mw/mn | Terminal functionality (f) |
| ????1 | ????6 | ????3520 | ????1.73 | |
| ????2 | ????12 | ????6750 | ????1.55 | |
| ????3 | ????15 | ????8920 | ????1.38 | ????2 |
Example 2
0.06g the solution of benzyl phenyl thioether in 4ml toluene is heated to 75 ℃, in 5 hours, add AIBN and vinyl acetate between to for plastic (0.0040g is in the 2ml vinyl acetate between to for plastic) continuously, reaction mixture is taken a sample in during certain, monomer adds the back what and kept 3 hours for 80 ℃, last monomer conversion is up to 95%, and detailed experiments the results are shown in Table 2.
Poly-(vinyl acetate between to for plastic) molecular weight of table 2 and the relation in reaction times
| Project | Time/h | Number-average molecular weight Mn | Molecular weight distribution mw/mn | Terminal functionality (f) |
| ????1 | ????3 | ????3720 | ????1.65 | |
| ????2 | ????5 | ????5950 | ????1.45 | |
| ????3 | ????8 | ????6920 | ????1.39 | ????2 |
Example 3
0.05g the solution of benzyl phenyl thioether in 8ml toluene is heated to 80 ℃, in 15 hours, add AIBN and vinylbenzene (0.0031g is in 10ml vinylbenzene) charging continuously, reaction mixture is taken a sample in during certain, after monomer adds, 90 ℃ of reactions of what 3 hours, last monomer conversion is up to 95%, and detailed results sees Table 3.
Table 3 polystyrene molecular weight and reaction times relation
| Project | Time/h | Number-average molecular weight Mn | Molecular weight distribution mw/mn | Terminal functionality (f) |
| ????1 | ????5 | ????13200 | ????1.63 | |
| ????2 | ????10 | ????23500 | ????1.57 | |
| ????3 | ????15 | ????31900 | ????1.39 | |
| ????4 | ????18 | ????35200 | ????1.31 | ????2 |
Example 4
0.05g the solution of benzyl phenyl thioether in 4ml benzene is heated to 60 ℃, in 8 hours, add AIBN and methyl methacrylate (0.0031g is in the 2ml methyl methacrylate) charging continuously, reaction mixture is taken a sample in during certain, after monomer adds, 60 ℃ of reactions of what 2 hours, last monomer conversion is up to 95%, and detailed results sees Table 4.
The molecular weight of table 4 polymethylmethacrylate and the relation in reaction times
| Project | Time/h | Number-average molecular weight Mn | Molecular weight distribution mw/mn | Terminal functionality (f) |
| ????1 | ????4 | ????5110 | ????1.74 | |
| ????2 | ????8 | ????7290 | ????1.51 | |
| ????3 | ????10 | ????8350 | ????1.43 | ????2 |
Example 5
0.05g the solution of benzyl phenyl thioether in 0.5ml toluene joins in sulfuric acid lauryl sodium salt (0.12g) de aerated water (10ml) solution that has stirred, then in 8 hours, add two (4-cyanopentanoic acid) and methacrylic tert-butyl acrylate (0.01g is in 4ml water and the 4ml methacrylic tert-butyl acrylate) chargings of 4.4 '-azo continuously, reaction mixture is taken a sample in during certain, monomer adds 80 ℃ of reactions of back what 3 hours, last monomer conversion is up to 95%, and experimental result sees Table 5 in detail.
The molecular weight of table 5 poly-(methacrylic tert-butyl acrylate) and the relation in reaction times
| Project | Time/h | Number-average molecular weight Mn | Molecular weight distribution mw/mn | Terminal functionality (f) |
| ????1 | ????4 | ????5230 | ????1.66 | |
| ????2 | ????8 | ????9770 | ????1.45 | |
| ????3 | ????10 | ????14300 | ????1.28 | ????2 |
Example 6
0.05g 80 ℃ of heating of the solution what of benzyl phenyl thioether in 5ml dimethyl formamide (DMF) added AIBN and vinylformic acid (0.0031g is in 2ml vinylformic acid) charging continuously in 6 hours.Reaction mixture during certain in sampling, after monomer adds, 80 ℃ of sustained reactions of what 3 hours, last monomer conversion is up to 95%, detailed experimental result sees Table 6.
The polyacrylic molecular weight of table 6 and the relation in reaction times
| Project | Time/h | Number-average molecular weight Mn | Molecular weight distribution mw/mn | Terminal functionality (f) |
| ????1 | ????3 | ????4740 | ????1.67 | |
| ????2 | ????6 | ????9150 | ????1.42 | |
| ????3 | ????9 | ????12700 | ????1.31 | ????2 |
Example 7
0.05g the solution what of benzyl phenyl thioether in 0.5ml toluene is heated to for 80 ℃ in degassing sulfuric acid fourth osmanthus base sodium salt (0.12g) water (10ml) solution that has stirred, in 8 hours, add 4.4 '-azo two (4-cyanopentanoic acid) and methacrylic tert-butyl acrylates (0.01g is in 4ml water and 4ml methacrylic tert-butyl acrylate) continuously, after monomer adds, 80 ℃ of sustained reactions of what 3 hours, add 2ml vinylbenzene then, reinforced lasting 8 hours, after monomer adds, 90 ℃ of sustained reactions of what 3 hours, last monomer conversion is up to 95%, and experimental result sees Table 7 in detail.
Table 7 gathers (methacrylic tert-butyl acrylate block styrene)
Molecular weight and the relation in reaction times
| Project | Time/h | Number-average molecular weight Mn | Molecular weight distribution mw/mn | Terminal functionality (f) |
| ????1 | ????11 | ????14300 | ????1.28 | |
| ????2 | ????22 | ????20700 | ????1.69 | ????2 |
Example 8
0.06g1.4-two (phenyl thioether methyl) benzene solution in 4ml toluene is heated to 80 ℃, in 12 hours, add AIBN and vinylbenzene (0.0031g is in 2ml vinylbenzene) charging, reaction mixture is taken a sample in during certain, after monomer has added, 90 ℃ of sustained reactions of what 3 hours, last monomer conversion is up to 95%, and detailed the results are shown in Table 8.
The relation in table 8 polystyrene molecular weight and reaction times
| Project | Time/h | Number-average molecular weight Mn | Molecular weight distribution mw/mn | Terminal functionality (f) |
| ????1 | ????6 | ????4700 | ????1.73 | |
| ????2 | ????12 | ????8670 | ????1.61 | |
| ????3 | ????15 | ????10100 | ????1.42 | ????2 |
After above-mentioned 8 embodiment polymerizations are finished, can from polymkeric substance, slough reaction medium and unreacted monomer, polymkeric substance is gone out fork-like farm tool used in ancient China or is precipitated out with non-solvent from watchman's clapper, after filtration, drying provides the user to use.Certainly also can directly provide polymers soln or emulsion to use according to purposes for the user.
The polymkeric substance of the present invention's preparation is suitable for what coating, tackiness agent and preparation of plates.The vindication primary coat, the face that can be used as automatic original equipment manufacturing are coated with and Clear coating, and various base material maintaining coatings for example are coated with steel, copper, brass and aluminium or non-metallic material as: timber, artificial and concrete etc. with what.
Claims (9)
1, the controllable free-radical polymerisation of thioether compound as chain transferring agent prepares the method that the polymer repeat unit structure has the polymkeric substance of general formula (A).
In the formula:
Z is a deutero-m valency residue from many groups that the aryl of any replacement is formed;
M be from
Maleic anhydride, N-methyl maleimide, N-aryl maleimide is selected arbitrarily in the polymer repeat unit structure of dialkyl fumarate and cyclic polymer conversion of monomer;
R is the alkyl from any replacement, and is saturated, unsaturated aromatic carbocyclic or heterocyclic ring, and alkyl sulfide, alkoxyl group, dialkyl amido is selected arbitrarily in the group that organo-metallic class and polymer chain are formed;
U is from hydrogen, the C that halogen replaces
1-C
4Alkyl, hydroxyl, alkoxyl group, carboxyl, acyloxy, the alcoxyl carboxyl is selected arbitrarily in the carboxylic acid ester groups;
V is from hydrogen, R ' CO
2H, CO
2R, COR ", CN, CONH
2, CONHR " and halogen in select arbitrarily;
Q is 〉=2 integer, and m is 〉=1 integer,
R ' is the alkyl from any replacement, chooses any one kind of them in the group that aryl and polymer chain are formed;
R " be C from any replacement
1-C
18Alkyl, C
2-C
18The alkane thiazolinyl, aryl, heterocyclic radical, aralkyl is chosen any one kind of them in the alkaryl, and the substituting group on the alkaryl can be separately from epoxy, hydroxyl, alkoxyl group, acyl group, acyl-oxygen, carbonic acid and carbonate, sulfonic acid and sulfonate, alcoxyl or fragrant oxygen-carbonyl, isocyanate group, itrile group, silyl is chosen any one kind of them in halogen and the dialkyl amido;
It is characterized in that general formula (A) polymkeric substance by:
(i) be CH from structure
2The vinyl monomer of=CUV, maleic anhydride, N-alkyl maleic anhydride, N-aryl maleic anhydride, choosing any one kind of them in dialkyl fumarate and the ring-type comonomer has the monomer of repeated structural unit M;
(ii) has general formula
Chain-transfer agent, should (C) formula in R be the free radical activity gene, S is a sulphur atom;
The radical source that (iii) produces free radical is in contact with one another prepared in reaction.
2, preparation method according to claim 1 is characterized in that: by changing (i) (ii) and the polydispersity of molar ratio controlling polymers (iii).
3, preparation method according to claim 1 is characterized in that: described general formula (A) and M polymer repeat unit structure are by the vinyl monomer in (i)
Be transformed.
4, preparation method according to claim 1 is characterized in that: the attribute of polymer repeat unit structure M and repeating unit numerical value m decision polymkeric substance, and when m 〉=1, when M was single monomer segment, then polymkeric substance was a homopolymer; When m 〉=2, be the segment from 2 or more a plurality of different monomers, selected when forming at the M of irregular sequence, then polymkeric substance is a multipolymer; When m 〉=2 and M choose any one kind of them from 2 or more a plurality of different monomers segment, its each different monomer segment or monomeric groups appear at discrete sequence, and then polymkeric substance is a segmented copolymer.
5, preparation method according to claim 1 is characterized in that: have general formula (C),
The thioether chain-transfer agent be from diphenyl sulfide, the benzyl phenyl thioether is chosen any one kind of them in two (phenyl thioether methyl) benzene.
6, preparation method according to claim 1 is characterized in that: described polymkeric substance is a random copolymers, segmented copolymer, graft copolymer, choosing any one kind of them in star copolymer and the ladder type multipolymer.
7, preparation method according to claim 6 is characterized in that: described polymer terminal group functionality is 2.
8, preparation method according to claim 1, it is characterized in that: the contact reacts of the radical source of vinyl monomer, chain-transfer agent and generation free radical is: what 40-160 ℃, vinyl monomer and radical source are added in the chain-transfer agent, reinforced time remaining 5-15 hour, what is 80-90 ℃ behind reinforced the finishing, and keeps 2-3 hour, and obtaining monomer conversion is 95%, the polymer dispersed degree is 1.31-1.69, and terminal functionality is 2 polymkeric substance.
Temperature when 9, vinyl monomer according to claim 8 and radical source are added to chain-transfer agent be 80 ℃ better.
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| CN 01132381 CN1260254C (en) | 2001-11-30 | 2001-11-30 | Controllable free radical polymerization process with thioether compound as chain transferring agent |
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| CN 01132381 CN1260254C (en) | 2001-11-30 | 2001-11-30 | Controllable free radical polymerization process with thioether compound as chain transferring agent |
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| CN1421466A true CN1421466A (en) | 2003-06-04 |
| CN1260254C CN1260254C (en) | 2006-06-21 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1301272C (en) * | 2004-10-25 | 2007-02-21 | 苏州大学 | Reversible addition-fragmentation chain transfer free radical polymerization method |
| CN102822211A (en) * | 2010-03-30 | 2012-12-12 | 巴斯夫欧洲公司 | End-functionalized polymers |
| CN109851695A (en) * | 2019-01-04 | 2019-06-07 | 中国矿业大学(北京) | A kind of chain-transferring agent and its preparation method and application |
| EP3686221A1 (en) * | 2015-12-28 | 2020-07-29 | Chevron Phillips Chemical Company LP | Mixed branched c20 sulfides compositions and use thereof as chain transfer agents |
-
2001
- 2001-11-30 CN CN 01132381 patent/CN1260254C/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1301272C (en) * | 2004-10-25 | 2007-02-21 | 苏州大学 | Reversible addition-fragmentation chain transfer free radical polymerization method |
| CN102822211A (en) * | 2010-03-30 | 2012-12-12 | 巴斯夫欧洲公司 | End-functionalized polymers |
| CN102822211B (en) * | 2010-03-30 | 2015-04-22 | 巴斯夫欧洲公司 | End-functionalized polymers |
| EP3686221A1 (en) * | 2015-12-28 | 2020-07-29 | Chevron Phillips Chemical Company LP | Mixed branched c20 sulfides compositions and use thereof as chain transfer agents |
| CN109851695A (en) * | 2019-01-04 | 2019-06-07 | 中国矿业大学(北京) | A kind of chain-transferring agent and its preparation method and application |
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| Publication number | Publication date |
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| CN1260254C (en) | 2006-06-21 |
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