CN100430430C - Benzooxazole kind block copolymer - Google Patents
Benzooxazole kind block copolymer Download PDFInfo
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- CN100430430C CN100430430C CNB200610116086XA CN200610116086A CN100430430C CN 100430430 C CN100430430 C CN 100430430C CN B200610116086X A CNB200610116086X A CN B200610116086XA CN 200610116086 A CN200610116086 A CN 200610116086A CN 100430430 C CN100430430 C CN 100430430C
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Abstract
This invention relates to a block copolymer of benzoxazoles, its made of chemical compound showed by formula(1), chemical compound hydrochlorate and phosphate showed by formula(2) and formula(3) as monomer. Its gained by copolymerization through following steps:(1) In the dehyd acid solvent, in condition of 120-200DEG C, chemical compound(1) and hydrochlorate or phosphate of compound(2) according to molar ratio (0.9-0.99):1 react 10-40 hours to produce prepolymer (i) solution; (2) In the dehyd acid solvent, in condition of 120-200DEG C, chemical compound(1) and hydrochlorate or phosphate of compound (2) according to molar ratio (0.005-0.1):1 react 10-40 hours to produce prepolymer (ii) solution; In condition of 150-250DEG C,prepolymer (i) solution and prepolymer (ii) solution produced by step(1) and step(2) react to extrude the Target product; Among the total; The dehyd acid solvent is methyl sulfonic acid, polyphosphate, chlorosulfonic acid, trifluoroacetic acid or/and concentrated sulfuric acid.The block copolymer of benzoxazoles provided by this invention possesses good flowability and Machining, and molecular mass can be controlled, overcoming the flaws existing in availability technique.
Description
Technical field
The present invention relates to a kind of Benzooxazole kind block copolymer.
Background technology
The benzoxazole base polymer is novel lyotropic liquid crystal macromolecular compound, and it is mainly form shown in formula (a) or the formula (b):
The benzoxazole base polymer has high strength, high-modulus, high temperature resistant and excellent properties that environmental stability is good, will become the requisite Material Useds of high-precision technical field such as medical science, electronics, information and space flight.
Currently reported benzoxazole base polymer, its repeating unit mostly are form shown in formula (a) or the formula (b) greatly.Adopt 4 as patent CN1644772A report, the polymerization in the medium of polyphosphoric acid (PPA) of 6-diamino resorcin hydrochlorate (DADHB) and terephthalic acid (TPA) obtains benzoxazole base polymer [form shown in the formula (b)].The major defect that exists in the prior art has two, the first, and the Benzooxazole kind polymer solution viscosity of acquisition is very big, causes its flowability and workability poor; It two is that the molecular weight of whole polymers is difficult to control in polymerization process.Therefore, how to overcome and have defective in the prior art, just become the technical issues that need to address of the present invention.
Summary of the invention
The objective of the invention is to, a kind of controlled Benzooxazole kind block copolymer of good fluidity and processibility and molecular weight that has is provided.
The present invention mainly is the polymer phase combination with formula (a) and formula (b) form, promptly reaches flowability and processibility and the controlled purpose of molecular weight of improving whole polymers (product) by obtaining a segmented copolymer.
The said Benzooxazole kind block copolymer of the present invention, it is a monomer with hydrochloric acid or the phosphoric acid salt by compound shown in compound shown in the formula (1), formula (2) and the formula (3), obtain [be called for short compound (1), all the other by that analogy] through the following step copolymerization with the compound shown in the following formula (1);
In the formula (1), Ar
1For
R
1With R
2Contraposition each other and being
Wherein: R
3Be OH, OR
4Or halogen, and R
4Be C
1-C
6Alkyl;
In the formula (2), Ar
2For
R
5With R
7Contraposition each other, R
6With R
8Contraposition each other,
Wherein: R
5, R
6Be NH
2, R
7, R
8Be OH;
In the formula (3), Ar
3For
R
9With R
11Contraposition each other, R
10With R
11Ortho position each other,
Wherein: R
9Be COOH, R
10, R
11Be selected from OH or NH respectively
2In a kind of and R
10≠ R
11
(1) in dehydrated solvent acid, the hydrochloride or the phosphoric acid salt of compound (1) and compound (2) is (0.9～0.99) in molar ratio: 1 reacted 10～40 hours under 120～200 ℃ of conditions, made prepolymer (i) solution;
Wherein, (preferred 0.5～7.0dl/g), its concentration is with 5wt.%～14wt.% (12wt.%～14wt.%) preferably that is advisable less than 10dl/g for the intrinsic viscosity of prepolymer (i);
(2) in dehydrated solvent acid, the hydrochloride or the phosphoric acid salt of compound (1) and compound (3) is (0.005～0.1) in molar ratio: 1 reacted under 120～200 ℃ condition 10～40 hours, made (ii) solution of prepolymer;
Wherein, (preferred 0.5～7.0dl/g), be advisable with 14wt.%～16wt.% by its concentration less than 10dl/g for prepolymer intrinsic viscosity (ii);
(3) prepolymer (i) solution that will make by step (1) and (2) and prepolymer (ii) solution extrude through reaction in 150～250 ℃ (preferred, 170～230 ℃) obtain target product (Benzooxazole kind block copolymer); It is better that the weight concentration of this segmented copolymer should be controlled at 6.5wt.%～16wt.%, best at 13wt.%～15wt.%.
Wherein: said dehydrated solvent acid can be selected methylsulphonic acid (MSA), polyphosphoric acid (PPA), chlorsulfonic acid (CSA), trifluoracetic acid (TFA), the vitriol oil strong protonic acid or its mixtures such as (SA) for use, and polyphosphoric acid is used in special recommendation.
Said herein substituting group " contraposition " each other is a generalized concept, promptly comprises said substituent with ring contraposition or different ring contraposition.
A preferred version of the present invention is: Ar
1Be phenyl (C
6H
4), R
3Be OH, Cl, Br or OR
4, and R
4Be C
1～C
3Alkyl; Best compound (1) is a terephthalic acid.
Another preferred version of the present invention is: Ar
2Be phenyl (C
6H
2), best compound (2) is 4, the 6-diamino resorcin.
Another preferred version of the present invention is: Ar
3Be phenyl (C
6H
3), best compound (3) is a 3-amino-4-hydroxy phenylformic acid.
Description of drawings
The infrared spectrum of prepolymer among Fig. 1 embodiment 1 (i);
Prepolymer infrared spectrum (ii) among Fig. 2 embodiment 1;
The shear viscosity of the whole polymers of Fig. 3 (product) and the graph of a relation of shear-stress;
The whole polymers of △-make by embodiment 1 described method wherein,
-whole the polymers that makes by comparative example 1 described method.
Embodiment
The said Benzooxazole kind block copolymer of the present invention, it is a monomer with the hydrochloride by compound shown in the compound shown in the formula (1), formula (2) and the formula (3), obtains through the following step copolymerization;
The hydrochloride of compound is sloughed evaporable hydrogenchloride earlier shown in formula (2) and the formula (3) before polymerization, promptly uses P
2O
5Content is that the polyphosphoric acid of 76wt.%～80wt.% carries out hydrogen chloride gas and removes in the time of 45～100 ℃;
(1) at P
2O
5Content is in the polyphosphoric acid of 80wt.%～90wt.%, the hydrochloride of compound (1) and the compound (2) through removing hydrogen chloride gas is (0.9～0.99) in molar ratio: 1 10～40 hours 120～200 ℃ of following reaction times of condition, made prepolymer (i) solution;
Wherein, the intrinsic viscosity of prepolymer (i) is 0.5～7.0dl/g, and the concentration of prepolymer (i) is 12wt.%～14wt.%;
(2) at P
2O
5Content is in the polyphosphoric acid of 80wt.%～90wt.%, the hydrochloride of compound (1) and the compound (3) through removing hydrogen chloride gas is (0.005～0.1) in molar ratio: 1 reacted 10～40 hours under 120～200 ℃ of conditions, made (ii) solution of prepolymer;
Wherein, prepolymer intrinsic viscosity (ii) is 0.5～7.0dl/g, and prepolymer concentration (ii) is 14wt.%～16wt.%;
(3) prepolymer (i) solution that will make by step (1) and (2) and prepolymer (ii) solution place in the same way the engagement type twin screw extruder (this forcing machine by two in the same way the screw rods of engagement form, contain the reverse thread groove on the forward screw thread, so that make material reach thorough mixing within a short period of time, thereby can improve the homogeneity of the molecular weight and the polymers soln of product), the screw speed of twin screw extruder is 10～200rpm, screw slenderness ratio is greater than 30 (generally being controlled at 40), react in 170～230 ℃ and to extrude, the residence time of material in twin screw extruder is 5～60 minutes (preferred 30 minutes), obtains target product.It is better that the weight concentration of this segmented copolymer should be controlled at 6.5wt.%～16wt.%, best at 13wt.%～15wt.%.
A kind of controlled Benzooxazole kind block copolymer of good fluidity and processibility and molecular weight that has is provided, has overcome the defective that exists in the prior art.Benzooxazole kind block copolymer solution energy spinning provided by the present invention or film forming, particularly when doing the spinning of spray-wet spinning technology, the fiber of available energy excellent (high-strength, Gao Mo and high temperature resistant), in addition, can also be as the toughener of thermosetting resin, rubber, plastics etc., be used for vest, flame resistant material or friction materials etc.
The invention will be further described below by embodiment, and its purpose only is better to understand content of the present invention, and unrestricted protection scope of the present invention:
Among the present invention, the intrinsic viscosity of prepolymer and whole polymers (product) is in the time of 30 ℃ to be that solvent adopts the intrinsic viscosity method to measure to obtain with the methylsulphonic acid.
Comparative example 1
Filling under the nitrogen condition, in the stirred autoclave of 10L, add 200g (0.9387mol) 4 successively, 6-diamino resorcin hydrochlorate, 151.26g (0.9105mol) terephthalic acid, the P of 674.75g
2O
5Content is the polyphosphoric acid of 80wt%, then reactor is sealed.Material is vacuumized, and logical then dry argon gas protection material makes the still internal pressure add to 0.2Mpa, under 60 ℃, stirs about 1.5h, makes mixing of materials even.Logical argon gas makes the still internal pressure reach 0.5Mpa in reactor, is warming up to 110 ℃ simultaneously, keeps 6 hours, opens purging valve, and the hydrogen chloride gas of effusion reclaims.Be warming up to 120 ℃ again, vacuumize and remove remaining hydrogen chloride gas, until using AgNO
3Solution checks that escaping gas can not produce white precipitate, returns to normal pressure then.Be cooled to below 40 ℃, in reactor, add 600gP
2O
5, material is vacuumized.Temperature of reaction is risen to 120 ℃ of reactions 4 hours, be warming up to 140 ℃ of reactions 6 hours again, be warming up to 160 ℃ of reactions 10 hours then.Obtain the prepolymer that intrinsic viscosity is 5.51dl/g (i) this moment.
It is 40 that above-mentioned prepolymer (i) solution and 5wt%TPA/PPA suspension distribution are got to length-to-diameter ratio with volume pump, internal diameter is in the twin screw extruder of 20mm, the rotating speed of control volume pump, the operational throughput that makes prepolymer is 60g/min, the operational throughput that makes TPA/PPA suspension simultaneously is 3.6g/min.Shearing force in forcing machine is 500S
-1, temperature is between 190～210 ℃, and the residence time is about 30 minutes, and the whole polymers intrinsic viscosity of gained is 25.84dl/g.Material through behind the volume pump, is done spray-wet spinning spinning, obtain the fiber that mean diameter is 20 μ m, its tensile strength is 4.5GPa, and stretch ratio is 35, and spinning temperature is 180 ℃.
Filling under the nitrogen condition, in the stirred autoclave of 10L, add 200g (0.9387mol) 4 successively, 6-diamino resorcin hydrochlorate, 151.26g (0.9105mol) terephthalic acid, the P of 674.75g
2O
5Content is the polyphosphoric acid of 80wt%, then reactor is sealed.Make the prepolymer A that intrinsic viscosity is 5.54dl/g by prepolymer preparation method in the comparative example 1, its infrared spectrum is seen Fig. 1.
Filling under the nitrogen condition, in the stirred autoclave of 2L, add 106.93g (0.564mol) 3-amino-4-hydroxy benzoate hydrochlorate successively, 4.69g (0.0282mol) terephthalic acid, the P of 178.93g
2O
5Content is the polyphosphoric acid of 80wt%, then reactor is sealed.Material is vacuumized, and logical then dry argon gas protection material makes the still internal pressure add to 0.2Mpa, under 60 ℃, stirs about 1.5h, makes mixing of materials even.Logical argon gas makes the still internal pressure reach 0.5Mpa in reactor, is warming up to 110 ℃ simultaneously, keeps 6 hours, opens purging valve, and the hydrogen chloride gas of effusion reclaims.Be warming up to 120 ℃ again, vacuumize and remove remaining hydrogen chloride gas, until using AgNO
3Solution checks that escaping gas can not produce white precipitate, returns to normal pressure then.Be cooled to below 40 ℃, in reactor, add 174.69gP
2O
5, material is vacuumized.Temperature of reaction is risen to 120 ℃ of reactions 4 hours, be warming up to 140 ℃ of reactions 16 hours again.Obtain the prepolymer B that intrinsic viscosity is 2.7l/g this moment, and its infrared spectrum is seen Fig. 2.
Prepolymer A solution and prepolymer B solution got to volume pump respectively length-to-diameter ratio is 40, internal diameter is in the twin screw extruder of engagement type in the same way of 20mm, the rotating speed of control volume pump, the operational throughput that makes prepolymer A is 60g/min, and the operational throughput that makes prepolymer B simultaneously is 17.2g/min.Shearing force in forcing machine is 500S
-1, temperature is between 190～210 ℃, and the residence time is about 30 minutes, and the gained intrinsic viscosity is the whole polymers of 29.53dl/g.This whole polymers through behind the volume pump, is done spray-wet spinning spinning, obtain the fiber that mean diameter is 15 μ m, its tensile strength is 4.4GPa, and stretch ratio is 35, and spinning temperature is 130 ℃.
The shear viscosity of the whole polymers of whole polymers of this routine gained and comparative example 1 and the relation of shear-stress are seen Fig. 3.As shown in Figure 3, the shear viscosity of the whole polymers of this routine gained (representing) with △ frequently than the whole polymers of example 1 (with
Expression) shear viscosity is little a lot, particularly under low shear-stress.Hence one can see that, and benzoxazole base polymer provided by the invention and existing Benzooxazole kind polymer phase ratio have better flowability and processibility.
Embodiment 2
Filling under the nitrogen condition, in the stirred autoclave of 10L, add 200g (0.9387mol) 4 successively, 6-diamino resorcin hydrochlorate, 151.26g (0.9105mol) terephthalic acid, the P of 674.75g
2O
5Content is the polyphosphoric acid of 80wt%, then reactor is sealed.Make the prepolymer C that intrinsic viscosity is 5.48dl/g by prepolymer preparation method in the comparative example 1.
Filling under the nitrogen condition, in the stirred autoclave of 2L, add 53.47g (0.282mol) 3-amino-4-hydroxy benzoate hydrochlorate successively, 4.69g (0.0282mol) terephthalic acid, the P of 89.47g
2O
5Content is the polyphosphoric acid of 80wt%, then reactor is sealed.Following reaction process operation is as embodiment 1.The degassing is cooled to below 40 ℃ after finishing, and adds 87.35gP in reactor
2O
5, material is vacuumized.Temperature of reaction is risen to 120 ℃ of reactions 4 hours, be warming up to 140 ℃ of reactions 16 hours again, obtaining intrinsic viscosity is the prepolymer D of 1.79dl/g.
It is 40 that prepolymer C solution and prepolymer D solution are got to length-to-diameter ratio with volume pump respectively, internal diameter is in the twin screw extruder of engagement type in the same way of 20mm, the rotating speed of control volume pump, the operational throughput that makes prepolymer C is 60g/min, the operational throughput that makes prepolymer D simultaneously is 8.66g/min.Shearing force in forcing machine is 500S
-1Temperature is between 190～210 ℃, the residence time is about 30 minutes, getting intrinsic viscosity is the whole polymers of 26.22dl/g, and whole polymers through behind the volume pump, is done spray-wet spinning spinning, obtain the fiber that mean diameter is 17 μ m, its tensile strength is 4.3GPa, and stretch ratio is 35, and spinning temperature is 130 ℃.
Claims (11)
1, a kind of Benzooxazole kind block copolymer, it is a monomer with hydrochloride or the phosphoric acid salt by compound shown in the compound shown in the formula (1), formula (2) and the formula (3), obtains through the following step copolymerization;
In the formula (1), Ar
1For
R
1With R
2Contraposition each other and being
Wherein: R
3Be OH, OR
4Or halogen, and R
4Be C
1-C
6Alkyl;
In the formula (2), Ar
2For
R
5With R
7Contraposition each other, R
6With R
8Contraposition each other, wherein: R
5, R
6Be NH
2, R
7, R
8Be OH;
In the formula (3), Ar
3For
Or
R
9With R
11Contraposition each other, R
10With R
11Ortho position each other, wherein: R
9Be COOH, R
10, R
11Be selected from OH or NH respectively
2In a kind of and R
10≠ R
11
(1) in dehydrated solvent acid, the hydrochloride or the phosphoric acid salt of compound (1) and compound (2) is (0.9～0.99) in molar ratio: 1 reacted 10～40 hours under 120～200 ℃ of conditions, made prepolymer (i) solution;
Wherein, the intrinsic viscosity of prepolymer (i) is less than 10dl/g, and the concentration of prepolymer (i) is 5wt.%～14wt.%;
(2) in dehydrated solvent acid, the hydrochloride or the phosphoric acid salt of compound (1) and compound (3) is (0.005～0.1) in molar ratio: 1 reacted under 120～200 ℃ condition 10～40 hours, made (ii) solution of prepolymer;
Wherein, prepolymer intrinsic viscosity (ii) is less than 10dl/g, and prepolymer concentration (ii) is 14wt.%～16wt.%;
(3) prepolymer (i) solution that will make by step (1) and (2) and prepolymer (ii) solution extrude the acquisition target product in 150～250 ℃ through reaction, the weight concentration of target product is 6.5wt.%～16wt.%;
Wherein: said dehydrated solvent acid is that methylsulphonic acid, polyphosphoric acid, chlorsulfonic acid, trifluoracetic acid are or/and the vitriol oil.
As the said benzoxazole base polymer of claim 1, it is characterized in that 2, wherein prepolymer (i) and prepolymer intrinsic viscosity (ii) are 0.5～7.0dl/g.
As the said benzoxazole base polymer of claim 1, it is characterized in that 3, wherein said dehydrated solvent acid is polyphosphoric acid.
As the said benzoxazole base polymer of claim 1, it is characterized in that 4, wherein the concentration of target product is 13wt.%～15wt.%.
5, as any said benzoxazole base polymer in the claim 1～4, it is characterized in that, wherein Ar
1For
R
3Be OH, Cl, Br or OR
4, and R
4Be C
1～C
3Alkyl.
As the said benzoxazole base polymer of claim 5, it is characterized in that 6, wherein used compound (1) is a terephthalic acid.
7, as any said benzoxazole base polymer in the claim 1～4, it is characterized in that, wherein Ar
2For
As the said benzoxazole base polymer of claim 7, it is characterized in that 8, wherein used compound (2) is 4, the 6-diamino resorcin.
9, as any said benzoxazole base polymer in the claim 1～4, it is characterized in that, wherein Ar
3For
As the said benzoxazole base polymer of claim 9, it is characterized in that 10, wherein used compound (3) is a 3-amino-4-hydroxy phenylformic acid.
As the said benzoxazole base polymer of claim 8, it is characterized in that 11, wherein used compound (3) is a 3-amino-4-hydroxy phenylformic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200610116086XA CN100430430C (en) | 2006-09-15 | 2006-09-15 | Benzooxazole kind block copolymer |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200610116086XA CN100430430C (en) | 2006-09-15 | 2006-09-15 | Benzooxazole kind block copolymer |
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| CN1948364A CN1948364A (en) | 2007-04-18 |
| CN100430430C true CN100430430C (en) | 2008-11-05 |
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| CNB200610116086XA Expired - Fee Related CN100430430C (en) | 2006-09-15 | 2006-09-15 | Benzooxazole kind block copolymer |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101914204B (en) * | 2010-06-17 | 2012-09-12 | 大连理工大学 | Polybenzoxazole based on dihydroxy diamine containing phthalazinone structure and preparation method thereof |
| CN110551284B (en) * | 2019-09-16 | 2022-01-14 | 浙江鼎龙科技股份有限公司 | Preparation method of poly (p-phenylene-benzobisoxazole) fibers |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1174430A1 (en) * | 2000-07-20 | 2002-01-23 | Universität Konstanz | Process for the preparation of heterocycles by using C1-building blocks |
| JP2003252993A (en) * | 2002-02-28 | 2003-09-10 | Sumitomo Bakelite Co Ltd | Heat-resistant resin precursor, heat-resistant resin and insulating film, and semiconductor device |
| CN1563151A (en) * | 2004-03-31 | 2005-01-12 | 华东理工大学 | Method for synthesizing polymer of benzoxazole class |
| CN1594398A (en) * | 2004-06-25 | 2005-03-16 | 东华大学 | Poly-benzobisoxazole polymer containing hydroxyl group and process for preparing same |
| EP1657274A1 (en) * | 2004-11-10 | 2006-05-17 | SOLVAY (Société Anonyme) | Polybenzazole block copolymer |
-
2006
- 2006-09-15 CN CNB200610116086XA patent/CN100430430C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1174430A1 (en) * | 2000-07-20 | 2002-01-23 | Universität Konstanz | Process for the preparation of heterocycles by using C1-building blocks |
| JP2003252993A (en) * | 2002-02-28 | 2003-09-10 | Sumitomo Bakelite Co Ltd | Heat-resistant resin precursor, heat-resistant resin and insulating film, and semiconductor device |
| CN1563151A (en) * | 2004-03-31 | 2005-01-12 | 华东理工大学 | Method for synthesizing polymer of benzoxazole class |
| CN1594398A (en) * | 2004-06-25 | 2005-03-16 | 东华大学 | Poly-benzobisoxazole polymer containing hydroxyl group and process for preparing same |
| EP1657274A1 (en) * | 2004-11-10 | 2006-05-17 | SOLVAY (Société Anonyme) | Polybenzazole block copolymer |
Non-Patent Citations (1)
| Title |
|---|
| 共轭刚棒苯并二噁唑类聚合物结构对其光物理性能的影响. 陈燕.2004年全国高分子材料科学与工程研讨会论文集. 2004 * |
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Granted publication date: 20081105 Termination date: 20110915 |