CN1047089A - The method for preparing radiactive and branching block copolymer - Google Patents
The method for preparing radiactive and branching block copolymer Download PDFInfo
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- CN1047089A CN1047089A CN 90102603 CN90102603A CN1047089A CN 1047089 A CN1047089 A CN 1047089A CN 90102603 CN90102603 CN 90102603 CN 90102603 A CN90102603 A CN 90102603A CN 1047089 A CN1047089 A CN 1047089A
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Abstract
(Z is the group that is derived from four sense couplers in the formula for radial pattern (star) that structural formula is following and branched block multipolymer; A is a polystyrene block; B is a polybutadiene block, and m, n, p, q are 1 or 0, and its summation is 1 to 4).Block copolymer composition comprises and diblock copolymer B-A and above-mentioned radial pattern of A homopolymer blended and branched block multipolymer.Disclose the method for preparing this radial pattern and branched block multipolymer and correspondent composition, and disclose them in bituminous composition, in order to improve the application of bituminous overall characteristic.
Description
The composition that the present invention relates to radial pattern (star) and branched block multipolymer and contain this multipolymer, and relate to their method of preparation and their application in bituminous composition.
In this technology, as everyone knows, in the presence of metal alkyl or metal aryl catalyzer, make the suitable monomer polymerization by the negatively charged ion method, and acquisition is fit to further " activity " superpolymer of conversion thereafter, " Garbanions, Living Polymers and El.Transfer Processes " (Interscience Publishers, J.Wiley ﹠amp as M.Shware; Sons, New York, 1968.) described in content.
By " activity " superpolymer technology, might prepare linearity or radial pattern segmented copolymer.For example, in linear block copolymers, can obtain A-B-A type polymkeric substance, wherein " A " is the polystyrene block with non-resilient thermoplastic properties, and " B " is the elasticity polybutadiene block.
Make reactive polymer and suitable coupler reaction, can obtain the radial pattern segmented copolymer.
As using under the silicon tetrachloride condition polymkeric substance that can obtain to be expressed from the next:
Si（B-A）
4
B and A can have the above connotation of defined in the formula.
In this technology, in order to improve the bituminous overall characteristic, especially improve performances such as its elasticity, viscosity and creep resistance behavior, the linear and application of radial pattern segmented copolymer in bituminous composition also is known.
For example, in the BE-738281 patent, disclose contain about 15%(weight) the bituminous composition of linear block copolymers A-B-A, wherein " A " is thermoplastic block (generally being polystyrene block), " B " is elastomeric block, generally is polybutadiene block.
The application of polystyrene-poly butadiene-type radial pattern segmented copolymer in bituminous composition and for example disclosed in the BE-853210 patent.
United States Patent (USP) 4464427 discloses and has contained the linear block copolymers that belongs to the above-mentioned type and the bituminous composition of radial pattern segmented copolymer.
As can be seen, introduce the radial pattern segmented copolymer in the bituminous composition, make the characteristics such as viscosity, elasticity and creep-resistant property of bituminous composition be better than using the performance of the bituminous composition of linear block copolymers.
The number of polymer segment is many more in the radial pattern multipolymer, and the effect of this improvement is big more.
Therefore, existing radial pattern segmented copolymer is preferably with polymer segment a large amount of and multifunctional coupler bonding.
When actual fabrication contained the radial pattern segmented copolymer that links to each other with described coupler more than 4, it was too high and limited its realization to run into many difficulties and/or cost but in fact.
The inventor has now found that and can break through the prior art level, and prepares and contain 4 radial pattern segmented copolymers with the polymer segment of four sense coupler bondings, it is characterized in that described polymer segment demonstrates the controllable degree of branching.
Radial pattern of the present invention can make the machinery-technical characteristic of the bituminous composition of wherein having introduced this multipolymer compare unforeseeable improvement with the composition of the corresponding radial pattern segmented copolymer that does not contain branching with the branched block multipolymer.
Another object of the present invention provides a kind of polymer composition that contains this radial pattern and branched block multipolymer.
A further object of the present invention provides preparation radial pattern and branched block multipolymer, and preparation contains the method for the polymer composition of this radial pattern and branched copolymers.
A further object of the invention provides the bituminous composition that contains this radial pattern and branched block multipolymer, or described polymer composition.
Other purposes of the present invention are more obvious through following explanation meeting.
The structure of radial pattern especially of the present invention and branched block multipolymer is as follows:
Z is the group that is derived from four sense couplers in the formula; A is a polystyrene block; B is a polybutadiene block; M, n, p, q or 1 or 0, condition is that the span of four sums is 1 to 4.
The molecular weight of polystyrene block " A " is generally in 10000 to 40000 scopes, and being good in 15000 to 25000 scopes.
The molecular weight of polybutadiene block " B " is generally in 20000 to 70000 scopes, and being good in 40000 to 50000 scopes.
M, n, p, q sum are being good in 1 to 3 scope.
Polymer composition of the present invention contains 50%(weight at least) above-mentioned radial pattern and branched block multipolymer, and to contain 60%(weight at least) for good, remainder is made of diblock copolymer B-A and " A " homopolymer, and wherein the connotation of " A " and " B " is as indicated above.
The method for preparing this polymer composition comprises the following steps (carrying out successively):
(a) catalyzer that uses metal alkyl or metal aryl compound to constitute, by reactive polymer technology in about 35 ℃ of polyreactions of carrying out styrene monomer to about 65 ℃ of temperature, the preparation molecular weight is 10000 to 40000 and contains polystyrene block with the atoms metal of polymkeric substance end of the chain bonding: " M " is the metal of metal alkyl or metal aryl catalyzer in the A-M(formula, and A is a polystyrene block);
(b) in the presence of polystyrene block (wherein the polymkeric substance end of the chain made of atoms metal and above-mentioned a step bonding) mutually, press reactive polymer technology, under about 60 ℃ to 100 ℃ temperature, carry out 1, the polyreaction of 3-divinylic monomer, with preparation diblock copolymer (wherein atoms metal and polyhutadiene end of the chain bonding): A-B-M, " A " is polystyrene block in the formula, " B " is polybutadiene block, the latter's molecular weight is 20000 to 70000, and the connotation of " M " is the same;
(c) in sufficiently long time of reaction mixture of 100 ℃ of (being generally 110 ℃ to 125 ℃) heating steps (b) preparations to about 140 ℃ temperature range, to produce the graft reaction of diblock copolymer B-A, and obtain grafted containing metal structure, it can be expressed from the next:
The connotation of A, B, M is the same;
(d) the containing metal structure coupling that step (c) is prepared with four sense couplers;
(e) reclaim polymeric material in the coupled reaction deutero-mixture by step (d), and optionally carry out (f) step,
(f) be separated in radial pattern and branched block multipolymer in the polymeric material that reclaims in the step (e).
A kind of embodiment form of recommending according to the present invention, ((step b) is that thermal insulation is carried out to cinnamic polyreaction, so that reach more than 100 ℃ in the last temperature of step (b), is up to 140 ℃ in the copolyreaction of step a) and later and divinyl.In order to obtain radial pattern of the present invention and branched copolymers, with copolyreaction later stage of divinyl, temperature should surpass 100 ℃ of this point and be absolutely necessary.
In fact, if be lower than 100 ℃ with the copolymerization latter temperature of divinyl, and when not being heated to the said temperature value again, the graft reaction of B-A multipolymer does not then take place on polyhutadiene B block, the final product after the coupling is nonbranched radial pattern multipolymer.
In implementation process, in order to obtain reactive polymer, requirement under anhydrous condition in the solution such as hexanaphthene and normal hexane equal solvent of inert hydrocarbon solvent, under about 50 ℃ initial temperature, use metal alkylide or metal arylide (especially n-Butyl Lithium or s-butyl lithium) to carry out cinnamic polyreaction (step a) as catalyzer, the scope of the mol ratio of vinylbenzene/catalyzer is 1000 to 5000, is good with 1500 to 2500.
Reaction continues about 60 minutes, transforms fully or transforms substantially fully until reaching cinnamic, and the molecular weight ranges of the polymer blocks that is obtained is 10000 to 40000, and is good with 15000 to 25000.
Adding 1 to containing in the polystyrene block solution of (containing atoms metal) under about 60 to 65 ℃ at the polymkeric substance end of the chain, the 3-divinyl, and in about 40 minutes clock times, obtain linear polymer B-A, wherein the molecular weight ranges of " B " block is 20000 to 70000, is good with 40000 to 50000.
To under the temperature more than 100 ℃, be incubated 10 to 20 minutes with the butadiene copolymer reaction solution that comes of deriving, temperature range be 110 ℃ to 125 ℃ better.
To mixture in add four sense couplers, can be selected from aliphatics and aromatic dicarboxylic acid ester class thereafter; The chlorinated derivative class of aliphatic hydrocarbon or aromatic hydrocarbon; The chlorinated derivative class of aliphatics or aromatic silane; The unsaturated aromatic hydrocarbon class that replaces is as Vinylstyrene; The tetrachloro of tin, silicon, germanium is for derivative, and with SiCl
4For good, SiCl
4/ cinnamic mol ratio equals its stoichiometric ratio or is similar to stoichiometric ratio.
In 100 ℃ to 140 ℃ temperature range, carried out coupled reaction 5 to 15 minutes, temperature be 110 ℃ to 125 ℃ better, general productive rate reaches 90% approximately.
In solution, add 1% to 1.5%(weight in the contained polymeric material) antioxidant, and reclaim this polymeric material in by reaction mixture through the solvent stripping, under 60 ℃, in vacuum drying oven, carry out drying.
Can be like this polymer composition that so obtains be added in the bituminous composition, or alternatively, radial pattern and branched copolymers and other polymeric materials are separated.
At least contain 50%(weight by (e) step derived polymers composition) radial pattern and branched copolymers, to contain 60%(weight at least) for good (constituting proportioning to 100%) by the styrene butadiene linear copolymer with by polyhutadiene.
With respect to accordingly not for the branching radial pattern polymkeric substance, radial pattern of the present invention and branched block multipolymer can make the mechanics of the bituminous composition that is added with this multipolymer and processing performance take place significantly to improve.
And, also can obtain to have the bituminous composition that is similar to the prior art characteristic by using consumption to be less than this multipolymer of the known consumption of prior art.
Can use 2 to 30 parts amount ranges to use this radial pattern of the present invention and branched block multipolymer by per 100 parts of (weight) pitches, it be good using 8 to 13 parts (weight) with per 100 parts of pitches.
The following example should be regarded as explanation of the present invention, and unrestricted connotation of the present invention.
Embodiment 1:
In the volume that agitator, thermometer and cooling jacket are housed with hot nitrogen dehumidifying is 1 liter reactor, adds 400 milliliters of anhydrous cyclohexanes and there is the vinylbenzene that descends to distill out in 15 grams (0.144 mole) by hydrolith.Hexanaphthene contains 0.035 gram THF.
Continue to stir this mixture down at 50 ℃.
Temperature is remained on 50 ℃, add 0.047 gram (0.73 mmole) s-butyl lithium as initiator of polyreaction, and sustained reaction 60 minutes, complete until styrene conversion.
After this, add 35 gram (0.648 mmole) 1,3-butadienes, and continued to carry out polyreaction 40 minutes.
The final temp of this polyreaction is 95 ℃.With formed segmented copolymer, promptly a kind of active copolymer was parked under 100 ℃ 1 minute, added 0.028 gram (0.165 mmole) SiCl then in reactor
4
This is reflected at and continues to carry out 15 minutes under 97 ℃, after this, the polymeric material that is obtained is equipped with in the glass flask of 45 gram Yoshinox BHTs (BHT) and phosphorous acid list two nonylbenzene mixed esters (Polygard) by one of reactor immigration.
This polymers soln of stripping under the vapour stream condition then, and in vacuum drying oven in 60 ℃ dry 2 hours down.
Characterize this polymer composition by gel permeation chromatography, it the results are shown in table 1.
Table 1
M Mw（AB）：70.10
3
Mw（AB）n：260.10
3
Mw/Mn（AB）：1.03
Mw/Mn（AB）n：1.02
Annotate: Mw-weight-average molecular weight, Mn-number-average molecular weight.
13 parts of polymer compositions are mixed mutually with 100 parts of pitches (SOLEA 180/200), use this polymer composition to prepare bituminous composition.
According to ASTMD5-65 and ASTMD36-66T standard, the characteristic of survey bituminous composition is listed in table 2.
Table 2
Viscosity (180 ℃) 2100 centipoises
125～130 ℃ of softening temperatures (global test)
Needling method hardness (Penetration) 40～45 decimillimeters
Embodiment 2:
Use the reagent with embodiment 1 same amount, but the initial temperature of styrene polymerization reaction is 60 ℃, reacts 20 minutes under adiabatic condition, the promotion to 65 of temperature of reaction ℃ when conversion of monomer is complete.
With copolyreaction latter stage of 1,3-butadiene because the influence of reaction release of heat, its temperature reaches 120 ℃.
With reaction later stage of divinyl, make polymers soln insulation 15 minutes at 120 ℃, the explanation of press embodiment 1 then, the interpolation silicon tetrachloride carries out this enforcement continuously.
The characteristic of this polymer composition is listed in table 3.
10 parts of polymer compositions are mixed mutually with 100 parts of pitches (SOLEA 180/200), use the polymer composition product to prepare bituminous composition.
The characteristic of thus obtained bituminous composition is listed in table 4(according to ASTM D5-65 and ASTM D36-66T standard testing).
Table 3
Mw（AB） 100.10
3
Mw（AB）n 330.10
3
Mw/Mn（AB） 1.4
Mw/Mn（AB）n 1.4
Table 4
Viscosity (180 ℃) 1700 centipoises
127 ℃ of softening temperatures (global test)
Needling method hardness 56 decimillimeters
Claims (6)
1, prepare the following radial pattern of a kind of general formula and the method for branched block multipolymer,
Z is the group that is derived from four sense couplers in the formula; A is that molecular weight ranges is 15000 to 40000 polystyrene block; B is that molecular weight ranges is 20000 to 70000 polybutadiene block; M, n, p, q or 1 or 0, its condition is that four summation spans are 1 to 4, it is characterized in that this method comprises to carry out the following step successively:
(a) catalyzer that uses metal alkyl or metal aryl compound to constitute, under 35 ℃ to 65 ℃ temperature, carry out the polyreaction of styrene monomer by reactive polymer technology, be 10000 to 40000 and contain polystyrene block with the atoms metal of polymkeric substance end of the chain bonding: A-M with the preparation molecular weight, " M " is the metal of metal alkyl or metal aryl catalyzer in the formula, and A is a polystyrene block;
(b) in the presence of polystyrene block (wherein atoms metal and the polymkeric substance end of the chain bonding) mutually, press reactive polymer technology, carry out the monomeric polyreaction of 1,3-butadiene, with preparation diblock copolymer (wherein atoms metal and polyhutadiene end of the chain bonding):
A-B-M, " A " is polystyrene block in the formula, and " B " is that molecular weight is 20000 to 70000 polybutadiene block, and the connotation of " M " is the same;
(c) be higher than under 100 ℃ the temperature heating by the sufficiently long time of reaction mixture of (b) step preparation, producing the graft reaction of diblock copolymer B-A, and obtaining grafted containing metal structure, this structure can be expressed from the next:
A-B
A-B-M
The connotation of A, B, " M " is the same in the formula;
(d) use the containing metal structure coupling for preparing by (c) step with four sense couplers;
(e) from the mixture of making by the coupled reaction of (d) step, reclaim polymeric material, and optionally carry out (f) step,
(f) separate by radial pattern and branched block multipolymer in the polymeric material that reclaims in the step (e).
2,, it is characterized in that in (a) step obtaining molecular weight and be 15000 to 25000 polystyrene block according to the method for claim 1.
3, according to the method for claim 1, it is characterized in that in (b) step, obtaining the B-A segmented copolymer, wherein the molecular weight of " A " is 15000 to 25000, the molecular weight of " B " is 40000 to 50000.
4,, it is characterized in that in (e) step in 110 ℃ to 125 ℃ temperature range internal heating reactive material 10 to 20 minutes according to the method for claim 1.
5,, it is characterized in that four sense couplers in (d) step are selected from aliphatics and aromatic dicarboxylic carboxylic ester ester class according to the method for claim 7; The chlorinated derivative class of aliphatic hydrocarbon or aromatic hydrocarbon; The chlorinated derivative class of aliphatics or aromatic silane; Unsaturated substituted arene class; The tetrachloro of tin, silicon, germanium is for derivatives class.
6,, it is characterized in that four sense couplers are SiCl according to the method for claim 5
4
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN87108076A CN1011972B (en) | 1986-12-01 | 1987-12-01 | Bituminous compositions which contain radial and branched block copolymers supplementary material |
Related Parent Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN87108076 Division | 1987-12-01 | ||
| CN87108076A Division CN1011972B (en) | 1986-12-01 | 1987-12-01 | Bituminous compositions which contain radial and branched block copolymers supplementary material |
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| Publication Number | Publication Date |
|---|---|
| CN1047089A true CN1047089A (en) | 1990-11-21 |
| CN1016695B CN1016695B (en) | 1992-05-20 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 90102603 Expired CN1016695B (en) | 1987-12-01 | 1987-12-01 | Preparation method of radiactive and branching block copolymer |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8586106B2 (en) | 2011-12-06 | 2013-11-19 | The Concentrate Manufacturing Company Of Ireland | Fatigue-relieving herbal extracts and beverages comprising the same |
| CN106433158A (en) * | 2016-07-07 | 2017-02-22 | 交通运输部科学研究院 | Preparation method of modified biological asphalt, modified biological asphalt and use thereof |
| CN110809508A (en) * | 2017-05-18 | 2020-02-18 | 科腾聚合物有限责任公司 | Asphalt composition and preparation method thereof |
-
1987
- 1987-12-01 CN CN 90102603 patent/CN1016695B/en not_active Expired
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8586106B2 (en) | 2011-12-06 | 2013-11-19 | The Concentrate Manufacturing Company Of Ireland | Fatigue-relieving herbal extracts and beverages comprising the same |
| CN106433158A (en) * | 2016-07-07 | 2017-02-22 | 交通运输部科学研究院 | Preparation method of modified biological asphalt, modified biological asphalt and use thereof |
| CN106433158B (en) * | 2016-07-07 | 2018-12-04 | 交通运输部科学研究院 | The preparation method of modification biological pitch and modification biological pitch and application thereof |
| CN110809508A (en) * | 2017-05-18 | 2020-02-18 | 科腾聚合物有限责任公司 | Asphalt composition and preparation method thereof |
| CN110809508B (en) * | 2017-05-18 | 2021-08-27 | 科腾聚合物有限责任公司 | Asphalt composition and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN1016695B (en) | 1992-05-20 |
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