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CN1298765C - Poly(ester-amide) containing isosorbide unit and process for preparing same - Google Patents

Poly(ester-amide) containing isosorbide unit and process for preparing same Download PDF

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Publication number
CN1298765C
CN1298765C CNB2005100798949A CN200510079894A CN1298765C CN 1298765 C CN1298765 C CN 1298765C CN B2005100798949 A CNB2005100798949 A CN B2005100798949A CN 200510079894 A CN200510079894 A CN 200510079894A CN 1298765 C CN1298765 C CN 1298765C
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Prior art keywords
diacid chloride
short
chloride
diacyl chloride
polyesteramide
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CN1702096A (en
Inventor
任鸿烽
宋莉芳
郭妙才
连彦青
王晓工
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Tsinghua University
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Tsinghua University
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Abstract

The present invention relates to polyesteramide containing isosorbitol units and a preparation method thereof, which belongs to the technical field of macromolecular materials. The structure of the polyesteramide is disclosed in the specification. The present invention uses the preparation method that a diamine monomer containg isosorbitol and ester bonds and diacid chloride are reacted to synthesize the polyesteramide. The polyesteramide prepared by the present invention has good solubility, good film forming performance and good mechanical property, and has the advantages of good thermal stability, high decomposition temperature and convenient machining. The present invention can be used in optical plastics, CD or DVD base materials, lenses, dashboard windows or hoods, prism reflectors, thin membranes, sheet materials, or optical fiber, etc. In addition, the polyesteramide has optical activity, and can be used in chiral stationary phases, chiral separation membranes, etc.

Description

Contain polyesteramide of isoscrbierite unit and preparation method thereof
Technical field
The invention belongs to technical field of polymer materials, particularly contain polyesteramide of isoscrbierite unit and preparation method thereof.
Background technology
Isosorbide (1,4:3,6-two dehydration-D-sorbyl alcohols) as the dewatered product of sorbyl alcohol, have abundant, the special advantages such as chirality feature, degradable and Heat stability is good of raw material sources, therefore great application prospect is arranged at aspects such as liquid crystal, optical plasticss.(the CN1298343 of E. I. Du Pont de Nemours and Co, CN1298346, CN1298416, CN1298417A, CN1298426) invented a series of polyester that contain Isosorbide, this polyester utilizes the condensation reaction of aromatic diacid and glycol, producing the polyester that reduced concentration viscosity is at least 0.15dL/g-0.35dL/g,, can obtain more full-bodied polyester with itself and other thermosetting polyester blend.Because its excellent properties, this polyester can be used to optical plastics, can make CD (CD), high definition CD (DVD), CD or base material (DVD), lens, panel board window or outer cover, prism reflector, film, sheet material or optical fiber etc.Patent CN1442460A has invented a kind of coating that contains Isosorbide, this coating utilizes the chirality feature of Isosorbide, can change and variable color with viewing angle, and have good anti-ultraviolet, acid and alkali-resistance, heat-resisting and weather resistance, can be applied to the external coating of multiple material.It is nuclear that patent US20020013483A has synthesized with the Isosorbide with Isosorbide and P-hydroxybenzoic acid, the product that two ends are hydroxyl.In addition, patent US20020115817A1, US20010003359A1, WO 03/027119A1 etc. has synthesized a series of vinylformic acid list dibasic acid esters that contain Isosorbide, these esters and some are had nematic liquid crystal monomer copolymerization, can obtain to have the cross linking membrane of cholesteryl phase, can be used for color filer.
Polymeric amide has excellent heat, power performance, and good chemical stability; But common aromatic polyamide is insoluble to general organic reagent usually, adopts the vitriol oil that processing units is had relatively high expectations in the course of processing, simultaneously, to some special occasions, has limited its application.
The applicant had once proposed name and had been called that " containing diamine monomer of di-dehydrated hexitol unit and preparation method thereof ", application number are 200410080283.1, publication number is: the patent application of CN1616462A, a kind of preparation method of diamine monomer is disclosed, comprising the preparation of the diamine monomer that contains Isosorbide.
Summary of the invention
The objective of the invention is to propose polyesteramide that contains isoscrbierite unit and preparation method thereof, utilize the disclosed technology of preparing that contains the unitary diamine monomer of two dewatering hexitols of the applicant, prepare the diamine monomer that contains Isosorbide, and further preparation contains the polyesteramide of isoscrbierite unit, to overcome the weak point of existing aromatic series or semiaromatic polyamide composition, make the polymeric amide of preparation have good solubility, film forming properties and mechanical property, have also that thermal stability is good, decomposition temperature is high, and process advantage easily.
The polyesteramide that contains isoscrbierite unit that the present invention proposes, the structure of this polyesteramide is:
Employing contains the diamine monomer and the diacid chloride reaction of Isosorbide, synthetic obtaining:
In the following formula, Ar ' is: In any,
R is any or multiple in the following structure:
Figure C20051007989400085
n＝2～10
n＝2～10
Figure C20051007989400087
R '=-CH3 or
Figure C20051007989400089
The above-mentioned preparation method who contains the polyesteramide of isoscrbierite unit may further comprise the steps:
(1) add polar solvent in containing the diamine monomer of isoscrbierite unit, additional proportion is: diamine monomer: polar solvent=1mol: 1L～4L;
(2) add earlier acid absorber in above-mentioned solution, add diacid chloride again, the mol ratio of adding is: diamine monomer: acid absorber: diacid chloride=1: 1: 0.9～1.1, under 0～60 ℃ and nitrogen protection, stirred 1～24 hour, and obtain the heavy-gravity polyamide solution.
Polar solvent in the aforesaid method is N, any in dinethylformamide, N,N-dimethylacetamide, N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO) or the hexamethylphosphoramide.
The diacid chloride of aforesaid method is that one or more of following classes of compounds use with any mixed:
Figure C20051007989400101
Be called for short diacid chloride A
Figure C20051007989400102
Be called for short diacid chloride B
Be called for short diacid chloride C
n＝2～16
Be called for short diacid chloride D
Figure C20051007989400105
n＝2～16
Be called for short diacid chloride E
Figure C20051007989400106
R=-CH3 or
Be called for short diacid chloride F
Figure C20051007989400108
Be called for short diacid chloride G
Be called for short diacid chloride H
(9)
Figure C20051007989400111
Be called for short diacid chloride I
Figure C20051007989400112
Be called for short diacid chloride J
Be called for short diacid chloride K
Figure C20051007989400114
Be called for short diacid chloride L
Figure C20051007989400115
Be called for short diacid chloride M
Be called for short diacid chloride N
Be called for short diacid chloride O
(16)
Figure C20051007989400121
Be called for short diacid chloride p
Acid absorber in the aforesaid method is that in pyridine or the triethylamine one or both use with any mixed.
For can be applicable to diacid chloride composition commonly used of the present invention, be not particularly limited usually, for example aromatic series diacid chloride and aliphatics diacid chloride and comprise above-mentioned deutero-diacid chloride.These diacid chloride compositions can be by the mixture use of two or more diacid chlorides alone or in combination.
The preparation method of the polyesteramide that contains Isosorbide of proposition of the present invention, owing to introduced alicyclic structure and Isosorbide has twist structure, therefore stop tightly packed between the molecular chain, increased the free volume of material, and then improved the solvability of material.The polymeric amide that synthetic contains Isosorbide generally has good solubility, dissolves in general polar solvent, and good film forming properties is arranged, and processing is convenient, can prepare film, fiber or the like.In addition, because the thermostability of Isosorbide, the synthetic polymeric amide has high glass transition, can be greater than 200 ℃, and thermal stability is good, and decomposition temperature can be greater than 400 ℃.Diacid chloride rigidity as employing is big, then can reach higher temperature.In addition, though introduced alicyclic structure, the alicyclic of Isosorbide has certain rigid, thereby has the good mechanical performance.In a word, the polymeric amide that contains Isosorbide can be used in the fields such as opticglass, optics, chiral separation owing to its excellent performance.
Embodiment
Embodiment 1
(1) add polar solvent N in containing the diamine monomer of Isosorbide, dinethylformamide, additional proportion are 1mol: 1L;
(2) in above-mentioned solution, add the acid absorber pyridine earlier; add diacid chloride A again, the mol ratio of adding is: diamines: pyridine: diacid chloride=0.9: 0.9: 1, stirred 1 hour under ice-water bath and nitrogen protection; room temperature reaction is 4 hours again, obtains the heavy-gravity polyamide solution.
Embodiment 2
(1) add the polar solvent N,N-dimethylacetamide in containing the diamine monomer of Isosorbide, additional proportion is 1mol: 2L;
(2) add the acid absorber pyridine earlier in above-mentioned solution, add diacid chloride B again, the mol ratio of adding is: diamines: pyridine: diacid chloride=1: 1: 1, under room temperature and nitrogen protection, stirred 1 hour, and obtain the heavy-gravity polyamide solution.
Embodiment 3
(1) add the polar solvent dimethyl sulfoxide (DMSO) in containing the diamine monomer of Isosorbide, additional proportion is 1mol: 3L;
(2) add earlier the acid absorber pyridine in above-mentioned solution, add diacid chloride C again, the mol ratio of adding is: diamines: pyridine: diacid chloride=1.1: 1.1: 1, under 60 ℃ and nitrogen protection, stirred 8 hours, and obtain the heavy-gravity polyamide solution.
Embodiment 4
(1) add the polar solvent N-Methyl pyrrolidone in the diamine monomer that contains Isosorbide of above-mentioned preparation, additional proportion is 1mol: 4L;
(2) add the acid absorber triethylamine earlier in above-mentioned solution, add diacid chloride D again, the mol ratio of adding is: diamines: triethylamine: diacid chloride=1.05: 1.05: 1, under room temperature and nitrogen protection, stirred 16 hours, and obtain the heavy-gravity polyamide solution.
Embodiment 5
(1) add the polar solvent N-Methyl pyrrolidone in containing the diamine monomer of Isosorbide, additional proportion is 1mol: 3L;
(2) add the acid absorber triethylamine earlier in above-mentioned solution, add diacid chloride E again, the mol ratio of adding is: diamines: triethylamine: diacid chloride=0.95: 0.95: 1, under room temperature and nitrogen protection, stirred 24 hours, and obtain the heavy-gravity polyamide solution.
Embodiment 6
(1) add the polar solvent hexamethylphosphoramide in containing the diamine monomer of Isosorbide, additional proportion is 1mol: 2L;
(2) in above-mentioned solution, add acid absorber triethylamine and pyridine earlier; add diacid chloride F again; the mol ratio that adds is: diamines: triethylamine: pyridine: diacid chloride=1.02: 0.51: 0.51: 1, under room temperature and nitrogen protection, stirred 18 hours, and obtain the heavy-gravity polyamide solution.
Embodiment 7: the diacid chloride monomer adopts diacid chloride G, and other technology is identical with embodiment 1.
Embodiment 8: the diacid chloride monomer adopts diacid chloride H, and other technology is identical with embodiment 1.
Embodiment 9: the diacid chloride monomer adopts diacid chloride I, and other technology is identical with embodiment 1.
Embodiment 10: the diacid chloride monomer adopts diacid chloride J, and other technology is identical with embodiment 1.
Embodiment 11: the diacid chloride monomer adopts diacid chloride K, and other technology is identical with embodiment 1.
Embodiment 12: the diacid chloride monomer adopts diacid chloride L, and other technology is identical with embodiment 3.
Embodiment 13: the diacid chloride monomer adopts diacid chloride M, and other technology is identical with embodiment 3.
Embodiment 14: the diacid chloride monomer adopts diacid chloride N, and other technology is identical with embodiment 2.
Embodiment 15: the diacid chloride monomer adopts diacid chloride O, and other technology is identical with embodiment 2.
Embodiment 16: the diacid chloride monomer adopts diacid chloride P, and other technology is identical with embodiment 2.
Embodiment 17: the diacid chloride monomer adopts diacid chloride P and diacid chloride E, and diacid chloride P: diacid chloride E: diamine monomer=0.5: 0.5: 1, other technology is identical with embodiment 2.
Embodiment 18: the diacid chloride monomer adopts diacid chloride B and diacid chloride D, and diacid chloride B: diacid chloride D: diamine monomer=0.1: 0.9: 1, other technology is identical with embodiment 2.
Embodiment 19: the diacid chloride monomer adopts diacid chloride B and diacid chloride D, and diacid chloride B: diacid chloride D: diamine monomer=0.8: 0.2: 1, other technology is identical with embodiment 2.
Embodiment 20: the diacid chloride monomer adopts diacid chloride D and diacid chloride M, and diacid chloride D: diacid chloride M: diamine monomer=0.2: 0.8: 1, other technology is identical with embodiment 4.
Embodiment 21: the diacid chloride monomer adopts diacid chloride D and diacid chloride M, and diacid chloride D: diacid chloride M: diamine monomer=0.4: 0.6: 1, other technology is identical with embodiment 4.
Embodiment 22: the diacid chloride monomer adopts diacid chloride D and diacid chloride I, and diacid chloride D: diacid chloride I: diamine monomer=0.1: 0.9: 1, other technology is identical with embodiment 5.
Embodiment 23: the diacid chloride monomer adopts diacid chloride K and diacid chloride I, and diacid chloride K: diacid chloride I: diamine monomer=0.9: 0.1: 1, other technology is identical with embodiment 5.
Embodiment 24: the diacid chloride monomer adopts diacid chloride K and diacid chloride I, and diacid chloride K: diacid chloride I: diamine monomer=0.4: 0.6: 1, other technology is identical with embodiment 5.
Embodiment 25: the diacid chloride monomer adopts diacid chloride J and diacid chloride D, and diacid chloride J: diacid chloride D: diamine monomer=0.4: 0.6: 1, other technology is identical with embodiment 5.
Embodiment 26: the diacid chloride monomer adopts diacid chloride J, diacid chloride B and diacid chloride D, and diacid chloride J: diacid chloride B: diacid chloride D: diamine monomer=0.4: 0.4: 0.2: 1, other technology is identical with embodiment 5.
Embodiment 27: the diacid chloride monomer adopts diacid chloride J, diacid chloride B and diacid chloride D, and diacid chloride J: diacid chloride B: diacid chloride D: diamine monomer=0.5: 0.2: 0.3: 1, other technology is identical with embodiment 5.

Claims (5)

1、一种含有异山梨醇单元的聚酯酰胺，其特征在于该聚酯酰胺的结构为：1, a kind of polyester amide containing isosorbide unit, it is characterized in that the structure of this polyester amide is:
Figure C2005100798940002C1
Figure C2005100798940002C1
 上式中，Ar’为： 或 中的任何一种，In the above formula, Ar' is: or any of the R为以下结构中的任何一种或多种：R is any one or more of the following structures: n＝2～10 n=2～10
Figure C2005100798940002C6
n＝2～10
Figure C2005100798940002C6
n=2～10 R′＝-CH3或者 R'=-CH3 or
Figure C2005100798940002C9
Figure C2005100798940002C9
 或or
Figure C2005100798940003C2
Figure C2005100798940003C2
 2、一种制备如权利要求1所述的含有异山梨醇单元的聚酯酰胺的方法，其特征在于该制备方法包括以下步骤：2. A method for preparing the polyester amide containing isosorbide units as claimed in claim 1, characterized in that the preparation method comprises the following steps: (1)在含有异山梨醇单元的二胺单体中加入极性溶剂，加入比例为：二胺单体∶极性溶剂＝1mol∶1L～4L；(1) Adding a polar solvent to the diamine monomer containing isosorbide units, the addition ratio is: diamine monomer: polar solvent = 1mol: 1L-4L; (2)在上述溶液中先加入酸吸收剂，再加入二酰氯，加入的摩尔比为：二胺单体∶酸吸收剂∶二酰氯＝1∶1∶0.9～1.1，在0～60℃和氮气保护下搅拌1～24小时，得到粘稠的聚酰胺溶液。(2) In the above solution, first add acid absorbent, then add diacid chloride, the molar ratio of adding is: diamine monomer: acid absorbent: diacid chloride=1: 1: 0.9～1.1, at 0～60 ℃ and Stir for 1-24 hours under nitrogen protection to obtain a viscous polyamide solution. 3、如权利要求2所述的方法，其特征在于，所述的极性溶剂为N，N-二甲基甲酰胺、N，N-二甲基乙酰胺、N-甲基吡咯烷酮、二甲基亚砜或六甲基磷酰胺中的任何一种。3. The method according to claim 2, wherein the polar solvent is N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl any of sulfoxide or hexamethylphosphoramide. 4、如权利要求2所述的方法，其特征在于，所述的二酰氯为以下各类化合物的一种或多种以任何比例混合使用：4. The method according to claim 2, wherein the diacid chloride is mixed with one or more of the following types of compounds in any proportion:
Figure C2005100798940004C1
简称二酰氯A
Figure C2005100798940004C1
Diacyl chloride A for short 简称二酰氯B Diacyl chloride B for short 简称二酰氯C Diacyl chloride C for short
Figure C2005100798940004C4
n＝2～16简称二酰氯D
Figure C2005100798940004C4
n=2～16 referred to as diacyl chloride D n＝2～16简称二酰氯E n=2～16 referred to as diacyl chloride E R＝-CH3或者 简称二酰氯F R=-CH3 or Diacyl chloride F for short
Figure C2005100798940004C8
简称二酰氯G
Figure C2005100798940004C8
Diacyl chloride G for short 简称二酰氯H Diacyl chloride H for short (9)(9) 简称二酰氯I Diacyl chloride I for short 简称二酰氯J Diacyl chloride for short
Figure C2005100798940005C3
简称二酰氯K
Figure C2005100798940005C3
Diacyl chloride K for short
Figure C2005100798940005C4
简称二酰氯L
Figure C2005100798940005C4
Diacyl chloride L for short 简称二酰氯M Diacyl chloride M for short 简称二酰氯N Abbreviated as diacyl chloride N 简称二酰氯O Diacyl chloride O for short (16)(16) 简称二酰氯P Diacyl chloride P for short 5、如权利要求2所述的方法，其特征在于其中所述的酸吸收剂为吡啶或三乙胺中的一种或两种以任何比例混合使用。5. The method according to claim 2, characterized in that the acid absorbent is one of pyridine or triethylamine or mixed in any proportion.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101648958B (en) * 2009-09-15 2011-11-16 清华大学 Preparation method of dianhydride monomer containing chiral dianhydro-hexitol
CN110911642B (en) * 2018-09-14 2021-05-11 多氟多化工股份有限公司 Binder for pole piece, preparation method of binder, silicon-based pole piece and lithium ion battery
CN111019126B (en) * 2019-12-06 2022-04-15 苏州大学 A kind of polyester amide and preparation method thereof
CN116004028B (en) * 2022-12-28 2024-07-02 江苏丽王科技有限公司 Preparation method of pigment yellow 180 mixed crystal
CN116178718A (en) * 2023-04-06 2023-05-30 常州大学 A kind of method of the polyimide of synthesizing long aliphatic chain

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1298343A (en) * 1998-04-23 2001-06-06 纳幕尔杜邦公司 Isosorbide containing polyesters and methods for making same
CN1298416A (en) * 1998-04-23 2001-06-06 纳幕尔杜邦公司 Polyesters including isosorbide as a comonomer and methods for making same
WO2003027119A1 (en) * 2001-09-24 2003-04-03 Koninklijke Philips Electronics N.V. Isosorbide derivatives

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1298343A (en) * 1998-04-23 2001-06-06 纳幕尔杜邦公司 Isosorbide containing polyesters and methods for making same
CN1298416A (en) * 1998-04-23 2001-06-06 纳幕尔杜邦公司 Polyesters including isosorbide as a comonomer and methods for making same
WO2003027119A1 (en) * 2001-09-24 2003-04-03 Koninklijke Philips Electronics N.V. Isosorbide derivatives

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