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WO2018196730A1 - 一种聚酯的制备方法 - Google Patents

一种聚酯的制备方法 Download PDF

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Publication number
WO2018196730A1
WO2018196730A1 PCT/CN2018/084185 CN2018084185W WO2018196730A1 WO 2018196730 A1 WO2018196730 A1 WO 2018196730A1 CN 2018084185 W CN2018084185 W CN 2018084185W WO 2018196730 A1 WO2018196730 A1 WO 2018196730A1
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cyclic monomer
same
pyridine
formula
monomer
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French (fr)
Inventor
郭凯
魏福兰
李振江
朱慧
陈思明
高宇
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Nanjing Tech University
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Nanjing Tech University
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Priority to US16/607,645 priority Critical patent/US11015021B2/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
    • C08G64/20—General preparatory processes
    • C08G64/30—General preparatory processes using carbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78—Preparation processes
    • C08G63/82—Preparation processes characterised by the catalyst used
    • C08G63/823—Preparation processes characterised by the catalyst used for the preparation of polylactones or polylactides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
    • C08G63/08—Lactones or lactides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/40—Polyesters derived from ester-forming derivatives of polycarboxylic acids or of polyhydroxy compounds, other than from esters thereof
    • C08G63/42—Cyclic ethers; Cyclic carbonates; Cyclic sulfites; Cyclic orthoesters

Definitions

  • the invention belongs to the technical field of organic catalysis and polymer materials, and particularly relates to a method for preparing polyester by using a pyridine saccharide salt.
  • Bioengineering materials are an important branch of biomedicine. They are an interdisciplinary subject of medicine, biology, and materials chemistry. They are precisely "inanimate materials that are used for medical purposes and are in contact with tissues to form functions.”
  • Polylactic acid, polycaprolactone, polyvalerolactone and polycarbonate are biodegradable and bioabsorbable polymer materials, which are easy to be blended with other polymer materials, and can improve the degradability of polymer materials.
  • the polylactic acid is prepared by a ring-opening polymerization of lactide using a metal-containing catalyst, such as CN1814644, CN1814645, and US5235031, US5357034, US4045418, US4057537, US3736646, and the like.
  • a metal-containing catalyst such as CN1814644, CN1814645, and US5235031, US5357034, US4045418, US4057537, US3736646, and the like.
  • these methods have a long reaction time, and the obtained polylactic acid cannot be applied to fields such as biomedicine and microelectronics because it is extremely difficult to remove metal residues.
  • the hydrogen bond catalyst has the characteristics of mild, high-efficiency, and no transesterification reaction, and obtains a low molecular weight distribution and a non-racemic polylactic acid. It is precisely because of the excellent properties possessed by hydrogen bond catalysis that finding a better hydrogen bond catalyst has great commercial application value.
  • the type of hydrogen bond is limited, only a small amount of bifunctional catalyst is used, and the synthesis of these bifunctional catalysts is now cumbersome.
  • the present invention finds problems and solves problems from practical needs, and synthesizes various kinds using organic hydrogen bond catalysts.
  • a biomolecular polymer of precise molecular weight Due to the deficiencies of DMAP catalysis, DMAP can be loaded with a carrier system in several ways but fewer methods are reported and the activity and recyclability of the catalyst cannot be simultaneously manifested.
  • the disadvantage of combining DMAP with nanomaterials is that very small amounts of catalyst can be recovered. Labeling with fluorine and recycling is good, but expensive.
  • the invention has obvious advantages such as mildness, high efficiency, wide source, simple synthesis, variety, wide range and no metal.
  • a method for preparing a polyester the steps of which are: the initiator alcohol initiates ring opening of a cyclic lactone monomer or a cyclic carbonate monomer, in the saccharin as shown in Formula I and the substituted pyridine as shown in Formula II Ring preparation to obtain a ring-opening polymerization of a small molecule catalyzed by a pyridine saccharide salt as shown in Formula III to obtain a polyester;
  • Said saccharin is as shown in formula I, substituted pyridine ring as shown in formula II, wherein R 1 , R 2 , R 3 are selected from N, N dimethylamino, pyrrolidinyl, hydrogen, having 1 to 10 carbons
  • R 1 , R 2 , R 3 are selected from N, N dimethylamino, pyrrolidinyl, hydrogen, having 1 to 10 carbons
  • R 1 when R 1 is selected from the group consisting of N,N-dimethylamino, pyrrolidinyl, and hydrogen, R 2 and R 3 may be independently selected from the group consisting of hydrogen, ethyl, isopropyl, and t-butyl. Or the same or different groups in the sec-butyl group; or the same or different groups having 1 to 10 carbon atoms and being a halogen atom, a hydroxyl group, a phenyl group and a substituted phenyl group;
  • R 1 , R 2 may be independently selected from the group consisting of hydrogen, ethyl, isopropyl, t-butyl or sec-butyl.
  • the pyridine saccharide salt catalyst as shown in Formula III is obtained by recrystallization of a saccharin as shown in Formula I and a substituted pyridine ring as shown in Formula II in a tetrahydrofuran solution at 60 ° C overnight.
  • the pyridine saccharide salt catalyst system of the present invention consists in that a substituted pyridine ring is mixed with saccharin in a tetrahydrofuran solution at 1:1, stirred at 60 ° C, and recrystallized by methanol and hexane.
  • the monomer is selected from one or more of the following:
  • A is [—(CR 1 R 2 )—] n , n is an integer from 2 to 10; R 1 and R 2 are selected from H, an alkyl group having 1 to 5 carbon atoms, and having 1 to 5 carbons. An alkyl group having an atom substituted by a halogen atom or a hydroxyl group, R 1 and R 2 are selected from the same or different groups; and X is selected from O or NH;
  • a and B are [—(CR 1 R 2 )—] n , n is an integer of 0-10, and A and B are the same or different; R 1 and R 2 are selected from H and have 1 to 5 carbon atoms.
  • X is selected from O or NH;
  • R 1 and R 2 are selected from H, an alkyl group having 1 to 5 carbon atoms and substituted by a halogen atom or a hydroxyl group, and R 1 and R 2 are selected from the same or different groups.
  • the catalyst of the present invention is prepared from a saccharin as shown in Formula I and a substituted pyridine ring as shown in Formula II to give a pyridine saccharide salt catalyst as shown in Formula III, representatively shown as number 13-22.
  • the cyclic monomer is as shown in formula (IV)
  • R 1 and R 2 are selected from H, X is selected from O, and the cyclic monomer is ⁇ -propiolactone;
  • R 1 and R 2 are selected from H, X is selected from O, and the cyclic monomer is ⁇ -butyrolactone;
  • R 1 and R 2 are selected from H, X is selected from O, and the cyclic monomer is ⁇ -valerolactone;
  • R 1 and R 2 are selected from H, X is selected from O, and the cyclic monomer is ⁇ -caprolactone;
  • R 1 and R 2 are selected from H, X is selected from O, and the cyclic monomer is macrocyclic undecanolactone;
  • R 1 and R 2 are selected from H, X is selected from NH, and the cyclic monomer is ⁇ -propiolactam;
  • R 1 and R 2 are selected from H, X is selected from NH, and the cyclic monomer is ⁇ -caprolactam;
  • R 1 is selected from a chlorine atom
  • R 2 is selected from H or R 1 is selected from H
  • R 2 is selected from a chlorine atom
  • X is selected from O and the cyclic monomer is chlorocaprolactone.
  • the cyclic monomer is as shown in formula (V)
  • R 1 is selected from methyl
  • R 2 is selected from H or R 1 is selected from H
  • R 2 is selected from methyl
  • X is selected from O
  • the cyclic monomer is lactide
  • R 1 is selected from bromine
  • R 2 is selected from H or R 1 is selected from H
  • R 2 is selected from bromine
  • X is selected from O
  • the cyclic monomer is bromoglycolide
  • R 1 is selected from methyl
  • R 2 is selected from H or R 1 is selected from H
  • R 2 is selected from methyl
  • X is selected from NH
  • cyclic monomer is 3,6- Dimethyl-oxo-oxocyclo-2,5-dione
  • R 1 is selected from methyl
  • R 2 is selected from H or R 1 is selected from H
  • R 2 is selected from methyl
  • X is selected from O
  • the cyclic monomer is butylated
  • R 1 is selected from methyl
  • R 2 is selected from H or R 1 is selected from H
  • R 2 is selected from methyl
  • X is selected from O
  • cyclic monomer is lactide
  • R 1 is selected from methyl
  • R 2 is selected from H or R 1 is selected from H
  • R 2 is selected from methyl
  • X is selected from O
  • cyclic monomer is macrocyclic ester.
  • n is 1 in A
  • n is 0 in B
  • R 1 and R 2 are selected from H
  • X is selected from N
  • the cyclic monomer is an N-carboxylic acid anhydride.
  • the monomers are trimethylene carbonate, hydroxytrimethylene carbonate, chlorotrimethylene carbonate.
  • the cyclic monomer of the present invention is shown in the structure of number 23-34:
  • the pyridine saccharide salt frees a small amount of pyridine under heating to co-catalyze the ring-opening polymerization of the cyclic lactone or carbonate to form a polyester, and the system has no other compound residue.
  • the pyridine saccharide salt catalyzes ring-opening polymerization of the cyclic lactone to obtain a polyester.
  • the present inventors have found that the difference in pyridine ring substituents will affect the catalytic efficiency.
  • the ring-opening polymerization needs to determine the appropriate temperature and temperature range according to the properties of the polymerization product and the process conditions of the polymerization reactor to ensure that the polymerization reaction proceeds efficiently within a certain temperature range.
  • the controlled distribution of the polyester end structure and molecular weight, for example, the narrow molecular weight distribution can be solved by adding an active hydrogen-containing compound (ROH) as a starter in the ring-opening polymerization reaction, and the monomer end structures induced by the RO- and -OH, and the ratio of lactone monomer to starter determines the target molecular weight of the resulting polyester.
  • ROH active hydrogen-containing compound
  • the pyridyl syrup salt is ring-opened and polymerized into living polymerization, and the obtained polymer contains no metal residue, and the molecular weight and terminal structure are controllable, and the molecular weight distribution is narrow.
  • the polyester process employs a bulk polymerization process, specifically comprising a cyclic lactone monomer or a cyclic carbonate monomer to the catalyst pyridine saccharide salt in a molar ratio of from 5 to 500, preferably from 20 to 200, particularly preferably from 30 to 150.
  • the reaction temperature is -50 to 200 ° C, preferably 50 to 180 ° C, particularly preferably 90 to 150 ° C; and the reaction time is 3 seconds to 120 hours, preferably 0.2 to 24 hours, particularly preferably 0.2 to 15 hours.
  • the initiator is an alcohol compound such as methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, benzyl alcohol, phenylethyl alcohol, ethylene glycol, ethylene glycol or pentaerythritol, preferably N-butanol, benzyl alcohol and phenylethyl alcohol.
  • the cyclic lactone monomer is lactide (LA), ⁇ -valerolactone;
  • the reaction can be carried out in an inert gas or under vacuum, the inert gas is preferably argon or nitrogen; the vacuum means that the pressure in the reactor is 4-20 mmHg; After dissolving with a good solvent and then purifying the solvent, such as methanol, ethanol or water, the good solvent is dichloromethane, chloroform, toluene, benzene, acetone or tetrahydrofuran, preferably dichloromethane, chloroform, tetrahydrofuran. .
  • the inert gas is preferably argon or nitrogen
  • the vacuum means that the pressure in the reactor is 4-20 mmHg
  • the good solvent is dichloromethane, chloroform, toluene, benzene, acetone or tetrahydrofuran, preferably dichloromethane, chloroform, tetrahydrofuran.
  • the present invention can efficiently synthesize precise polyester (polylactic acid, polyvalerolactone) by the above catalytic system, and has wide application compared with the synthetic polyester containing metal catalyst (stannous octoate) in the prior art. It has no metal residue, narrow molecular weight distribution and no chain transesterification reaction, and has great commercial application potential in the field of biomedicine and microelectronics.
  • the present invention catalyzes a polymerization reaction by a hydrogen bond by the above catalytic system, and has higher catalytic efficiency than the organically-catalyzed strong acid (trifluoromethanesulfonic acid) and strong base (N-heterocyclic carbene) which have been reported. More gentle features.
  • dimethylaminopyridinose salt (DMAP ⁇ saccharin) is synthesized by a commercially available one-step reaction of saccharin and a pyridine ring, and is obtained by recrystallization from methanol and hexane. And does not have the skin toxicity of DMAP, it can be recycled.
  • the product can be controlled to synthesize the target molecular weight product polylactic acid, the molecular weight distribution index is narrow, the product yield is high, no monomer remains, and the color is white.
  • the present invention has advantages over existing catalyst systems such as mildness, high efficiency, wide source, simple synthesis, various types, wide range, and no metal.
  • Figure 1 1 H NMR spectrum of polylactic acid prepared by using 4-(N,N-dimethylamino)pyridinose salt as a catalyst;
  • Figure 2 Spectra of polylactic acid prepared by using 4-(N,N-dimethylamino)pyridinose salt as a catalyst in size exclusion chromatography;
  • Figure 3 1 H NMR spectrum of polyvalerolactone prepared by using 4-(N,N-dimethylamino)pyridinose salt as a catalyst;
  • Figure 4 Spectra of polyvalerolactone prepared by using 4-(N,N-dimethylamino)pyridinose salt as a catalyst in size exclusion chromatography;
  • valerolactone 0.288 g, 2.88 mmol
  • benzyl alcohol 10 ⁇ l, 0.096 mmol
  • compound No. 14 0.0375 g, 0.096 mmol
  • magnetic stirring 90 ° C for 1 h
  • the obtained crude product was dissolved in a minimum amount of dichloromethane, and then added to a cold methanol solution to precipitate a polymer.
  • 0.21 g of a white solid was obtained, which was transferred to a vacuum oven and dried.
  • the polymer structure was identified by 1 H NMR and 13 C NMR, and the molecular weight and dispersion of the polymer were determined by GPC.
  • the compound of the invention No. 14 was added to a 250 ml reaction flask, and the compound of the formula 2 (12.27 mmol, 1.5 g), saccharin (12.27 mmol, 1.5 g) was stirred in a tetrahydrofuran (THF) solution at 60 ° C overnight. reaction. The solvent was removed under vacuum to give a crude material. Methanol (10 ml) and hexane (20 ml) were recrystallized to give white crystals. Filter and dry before use.
  • THF tetrahydrofuran
  • the compound of the invention No. 16 was added to a 250 ml reaction flask, and the compound of No. 4 (12.27 mmol, 1.5 g), saccharin (12.27 mmol, 1.5 g) was stirred in a tetrahydrofuran (THF) solution at 60 ° C overnight. reaction. The solvent was removed under vacuum to give a crude material. Methanol (10 ml) and hexane (20 ml) were recrystallized to give white crystals. Filter and dry before use.
  • THF tetrahydrofuran
  • the polymer structure was identified by 1 H NMR and 13 C NMR, and the molecular weight and dispersion of the polymer were determined by GPC. It was determined that the polymer conversion was 93.4%, a number-average molecular weight M n 12100g mol -1, M n / M w 1.36.
  • the compound of the present invention, No. 19, was added to a 250 ml reaction flask, and the compound of No. 7 (12.27 mmol, 1.5 g), saccharin (12.27 mmol, 1.5 g) was stirred in a tetrahydrofuran (THF) solution at 60 ° C overnight. reaction. The solvent was removed under vacuum to give a crude material. Methanol (10 ml) and hexane (20 ml) were recrystallized to give white crystals. Filter and dry before use.
  • THF tetrahydrofuran
  • the polymer structure was identified by 1 H NMR and 13 C NMR, and the molecular weight and dispersion of the polymer were determined by GPC. It was determined that the polymer conversion was 98.4%, a number-average molecular weight M n 4400g mol -1, M n / M w 1.13.
  • the compound of the invention, No. 13 was added to a 250 ml reaction flask, and the compound of No. 1 (12.27 mmol, 1.5 g), saccharin (12.27 mmol, 1.5 g) was stirred in a tetrahydrofuran (THF) solution at 60 ° C overnight. reaction. The solvent was removed under vacuum to give a crude material. Methanol (10 ml) and hexane (20 ml) were recrystallized to give white crystals. Filter and dry before use.
  • THF tetrahydrofuran

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Abstract

本发明公开了一种聚酯的制备方法，属于有机催化和高分子材料技术领域，本发明的制备方法(1)吡啶糖精盐在60℃条件下吡啶和糖精(1:1)在四氢呋喃中制备，在甲醇和己烷中析出。(2)吡啶糖精盐在加热状态下游离出少量吡啶二者共同催化环状内酯或碳酸酯开环聚合形成聚酯，体系没有其他化合物残留。(3)在醇类起始剂的存在下，吡啶糖精盐催化环状内酯开环聚合得到聚酯。通过上述催化体系能够高效合成精确的聚内酯，相比已有的技术中含金属催化剂的合成聚酯，具有广泛应用型，且具有无金属残留，分子量分布窄，无链转酯反应，对于生物医药领域和微电子领域具有很大商业应用潜力。

Description

一种聚酯的制备方法 技术领域
本发明属于有机催化和高分子材料技术领域，具体涉及用吡啶糖精盐制备聚酯的方法。
背景技术
生物工程材料是生物医学的重要分支,它是医学、生物和材料化学的交叉学科,准确的说是“以医疗为目的,用于与组织接触以形成功能的无生命的材料”。聚乳酸、聚己内酯、聚戊内酯和聚碳酸酯作为生物可降解、可生物吸收的高分子材料，易于与其他高分子材料共混制备，可改善高分子材料的可降解性。作为来源于可再生资源农作物的全降解环保材料，已经引起了全世界人们的广泛关注和研究。
聚酯的制备方法目前已有大量的研究，其中用环状内酯进行开环聚合是研究较多的一种方法。就用于丙交酯开环聚合的催化剂而言，早期使用含金属的催化剂对丙交酯进行开环聚合来制备聚乳酸，如CN1814644、CN1814645和US5235031、US5357034、US4045418、US4057537、US3736646等专利。但是这些方法反应时间较长，并且制得的聚乳酸由于极难除去金属残留物，因而无法应用于生物医学和微电子等领域。后来Connor等(FredrikNederber等.AngewandteChemie International Edition,2001,40,2712-2715)提出用有机催化剂来催化丙交酯开环聚合来制备聚乳酸，并尝试了用4- 二甲氨基吡啶作为催化剂。但是4-二甲氨基吡啶不仅会残留于聚合物中，而且还具有严重的皮肤毒性。为了避免有害化学试剂排放到环境中，发现由4-二甲氨基吡啶(DMAP)形成的盐很容易从产物中分离，并且可以循环使用。
2001年，Hedrick研究了用氢键催化开环聚合的工作。有机催化剂就效率和范围而言，已经成为可以替代金属催化和酶催化的全面催化剂。氢键催化剂具有温和、高效、无转酯反应的特点，得到低的分子量分布和无消旋的聚乳酸。正是因为氢键催化拥有的优良特性，找到更好的氢键催化剂拥有很大的商业应用价值。目前氢键的种类限制，仅有少量的双功能团的催化剂，而且现在这些双功能催化剂的合成比较繁琐。
为了满足生物医学领域和微电子领域对材料的要求和简单、温和、高效合成精确分子量的聚合物的要求，本发明从实际的需求中去发现问题和解决问题，利用有机氢键催化剂合成多种精确分子量的生物可降解性的高分子聚合物。由于DMAP催化的不足，可以采取的几种方式，用载体系统装载DMAP但是较少的方法被报道而且催化剂的活性和可回收性不能够同时体现。用纳米材料结合DMAP，缺点是很少量的催化剂可以被回收。用氟标记并且进行回收的效果很好，但是费用昂贵。为了克服上述方法的不足，有必要引入一种结构稳定，使用方便，能够很好地控制聚合过程，且安全无冗余的残留的催化剂。如式Ⅲ所示化合物，二者通过氢键结合为七元环合成子的稳定结构进行催化，具有明显的优势，所得的聚合物的具有分子量分布窄的特点
发明内容
本发明的目的在于提供一种聚酯的制备方法，一类基于吡啶糖精盐催化体系催化环状内酯的开环聚合。本发明相比现有的催化体系具有温和、高效、来源广、合成简单、种类多、范围广、不含金属等明显的优势。
一种聚酯的制备方法，其步骤为：引发剂醇引发环状内酯单体或环状碳酸酯单体的开环，在如式Ⅰ所示的糖精和如式Ⅱ所示的取代吡啶环制备得到如式III所示的吡啶糖精盐催化下引发小分子单体的开环聚合，得到聚酯；
Figure PCTCN2018084185-appb-000001
Figure PCTCN2018084185-appb-000002
所述的糖精如式Ⅰ所示，取代吡啶环如式Ⅱ所示，其中R 1，R 2，R 3选自N,N二甲基氨基，吡咯烷基，氢，具有1～10个碳原子的烷基，具有1～10个碳原子的烷基并被卤原子、羟基、苯基或取代苯基中的一种或多种相同或不同基团所取代。
式Ⅱ中，当R 1选自N,N-二甲基氨基，吡咯烷基，氢中的一种，R 2、R 3可分别选自为氢，乙基，异丙基，叔丁基或仲丁基中的相同或不同 基团；或者是具有1～10个碳原子并被卤原子、羟基，苯基和取代苯基中相同或不同基团；
当R 3选自N,N-二甲基氨基，吡咯烷基，氢中的一种，R1、R 2可分别选自氢，乙基，异丙基，叔丁基或仲丁基中的相同或不同基团；或者是具有1～10个碳原子并被卤原子、羟基，苯基和取代苯基中相同或不同基团。
优选如式Ⅱ所示的取代吡啶环如编号1-12所示的结构
Figure PCTCN2018084185-appb-000003
所述的如式III所示的吡啶糖精盐催化剂由如式Ⅰ所示的糖精和如式Ⅱ所示的取代吡啶环在60℃的四氢呋喃溶液中过夜重结晶得到。
本发明的吡啶糖精盐催化体系在于被取代的吡啶环与糖精在四 氢呋喃溶液中1：1混合在60℃下搅拌，通过甲醇和己烷重结晶析出。
所述的单体选自以下一种或几种：
(1)
Figure PCTCN2018084185-appb-000004
其中，A为[—(CR 1R 2)—] n，n为2-10的整数；R 1、R 2选自H、具有1-5个碳原子的烷基、具有1-5个碳原子并被卤原子或羟基取代的烷基，R 1、R 2选自相同或不相同基团；X选自O或NH；
(2)
Figure PCTCN2018084185-appb-000005
其中，A、B为[—(CR 1R 2)—] n，n为0-10的整数，A和B相同或不同；R 1、R 2选自H、具有1-5个碳原子的烷基、具有1-5个碳原子并被卤原子或羟基取代的烷基，R 1、R 2选自相同或不相同基团；X选自O或NH；
(3)三亚甲基碳酸酯以及如式(VI)所示的的环状碳酸酯
Figure PCTCN2018084185-appb-000006
其中，R 1、R 2选自H、具有1～5个碳原子并被卤原子或羟基取代的烷基，R 1、R 2选自相同或不相同基团。
本发明所述的催化剂由如式Ⅰ所示的糖精和如式Ⅱ所示的取代吡啶环制备得到如式Ⅲ所示的吡啶糖精盐催化剂，代表性地，如编号13-22所示。
Figure PCTCN2018084185-appb-000007
Figure PCTCN2018084185-appb-000008
所述的环状单体如式(IV)所示
Figure PCTCN2018084185-appb-000009
其中，A为[—(CR 1R 2)—] n
当n＝2，R 1、R 2选自H，X选自O，环状单体为β-丙内酯；
当n＝3，R 1、R 2选自H，X选自O，环状单体为γ-丁内酯；
当n＝4，R 1、R 2选自H，X选自O，环状单体为δ-戊内酯；
当n＝5，R 1、R 2选自H，X选自O，环状单体为ε-己内酯；
当n＝10，R 1、R 2选自H，X选自O，环状单体为大环十一内酯；
当n＝2，R 1、R 2选自H，X选自NH，环状单体为β-丙内酰胺；
当n＝5，R 1、R 2选自H，X选自NH，环状单体为ε-己内酰胺；
当n＝5，R 1选自氯原子，R 2选自H或R 1选自H，R 2选自氯原子，
X选自O，环状单体为氯代己内酯。
所述的环状单体如式(V)所示
Figure PCTCN2018084185-appb-000010
其中，A、B为[—(CR 1R 2)—] n
当n＝1，A和B相同，R 1、R 2选自H，X选自O，环状单体为乙交酯；
当n＝1，A和B相同，R 1选自甲基，R 2选自H或R 1选自H，R 2选自甲基，X选自O，环状单体为丙交酯；
当n＝1，A和B相同，R 1选自溴，R 2选自H或R 1选自H，R 2选自溴，X选自O，环状单体为溴代乙交酯；
当n＝1，A和B相同，R 1选自甲基，R 2选自H或R 1选自H，R 2选自甲基，X选自NH，环状单体为3,6-二甲基对氧氮己环-2,5-二酮；
当n＝2，A和B相同，R 1选自甲基，R 2选自H或R 1选自H，R 2选自甲基，X选自O，环状单体为丁交酯；
当n＝8，A和B相同，R 1选自甲基，R 2选自H或R 1选自H，R 2选自甲基，X选自O，环状单体为癸交酯；
当n＝10，A和B相同，R 1选自甲基，R 2选自H或R 1选自H，R 2选自甲基，X选自O，环状单体为大环十交酯。
当A和B不同，A中n＝1，B中n＝0，R 1、R 2选自H，X选自O，环状单体为O-羧酸内酸酐；
当A和B不同，A中n＝1，B中n＝0，R 1、R 2选自H，X选自N，环状单体为N-羧酸内酸酐。
所述的单体为三亚甲基碳酸酯、羟基三亚甲基碳酸酯、氯代三亚甲基碳酸酯。
本发明所述环状单体，代表性地，如编号23-34结构所示：
Figure PCTCN2018084185-appb-000011
为了解决上述技术问题，本发明的思路如下：
(1)吡啶糖精盐在60℃条件下吡啶和糖精(1:1)在四氢呋喃中制备，在甲醇和己烷中析出。
(2)吡啶糖精盐在加热状态下游离出少量吡啶二者共同催化环状内酯或碳酸酯开环聚合形成聚酯，体系没有其他化合物残留。
(3)在醇类起始剂的存在下，吡啶糖精盐催化环状内酯开环聚合得到聚酯。
本发明经研究发现，吡啶环取代基的不同，将影响催化效率。开 环聚合反应，需根据聚合产物的性状要求以及聚合反应装置的工艺条件来确定适宜温度及温度变化范围，保证聚合反应在一定温度范围内有效的进行。
聚酯末端结构和分子量的可控分布，例如窄分子量分布可以通过开环聚合反应中加入含活泼氢的化合物(R-O-H)作为起始剂来解决，其引发的单体末端结构分别为R-O-和-OH，而内酯单体与起始剂的比例决定了所得聚酯的目标分子量。在有起始剂的条件下，吡啶糖精盐开环聚合为活性聚合，所得的聚合物不含金属残留物，分子量和末端结构可控，分子量分布窄。
本发明的技术方案如下：
所述的聚酯方法采用本体聚合法，具体包括环状内酯单体或环状碳酸酯单体与催化剂吡啶糖精盐的摩尔比为5-500，优选20-200，特别优选30-150。反应温度为-50-200℃，优选为50-180℃，特别优选90-150℃；反应时间为3秒-120小时，优选为0.2-24小时，特别优选0.2-15小时。
所述的引发剂为醇类化合物，例如甲醇，乙醇，正丙醇，异丙醇，正丁醇，叔丁醇，苯甲醇，苯乙醇，乙二醇，缩乙二醇或季戊四醇，优选为正丁醇，苯甲醇和苯乙醇。所述环状内酯单体为丙交酯(LA)、δ-戊内酯；
在本体聚合法中，反应可以在惰性气体中或真空下进行，所述的惰性气体优选为氩气或氮气；所述的真空是指反应器内压力为4-20毫米汞柱；反应产物优选用良溶剂溶解后再沉出溶剂，例如甲醇，乙 醇或水中纯化，所述的良溶剂为二氯甲烷、三氯甲烷、甲苯、苯、丙酮或四氢呋喃，优选二氯甲烷、三氯甲烷、四氢呋喃。
有益效果：
(1)本发明通过上述催化体系能够高效合成精确的聚酯(聚乳酸、聚戊内酯)，相比已有的技术中含金属催化剂的合成聚酯(辛酸亚锡类)，具有广泛应用型，且具有无金属残留，分子量分布窄，无链转酯反应，对于生物医药领域和微电子领域具有很大商业应用潜力。
(2)本发明通过上述催化体系通过氢键的作用催化聚合反应，相比已有报道的有机催化强酸(三氟甲磺酸)和强碱(N-杂环卡宾)类，催化效率高，更具有温和的特点。
(3)本发明中通过商业可得糖精和吡啶环类一步反应合成二甲基氨基吡啶糖精盐(DMAP·saccharin)，通过甲醇和己烷进行重结晶得到。并且不具有DMAP的皮肤毒性，可回收。
(4)此工艺可根据需求，受控的合成目标分子量的产品聚乳酸，分子量分布指数较窄，产品产率高，无单体残留，色泽雪白。
综上所述，本发明相比现有的催化体系具有温和、高效、来源广、合成简单、种类多、范围广、不含金属等明显的优势。
附图说明
结合附图来详细说明本发明的实施例，其中
图1：用4-(N,N-二甲基氨基)吡啶糖精盐作催化剂制备得到的聚乳酸的 1H NMR谱图；
图2：用4-(N,N-二甲基氨基)吡啶糖精盐作催化剂制备得到的聚乳酸在体积排阻色谱分析中的谱图；
图3：用4-(N,N-二甲基氨基)吡啶糖精盐作催化剂制备得到的聚戊内酯的 1H NMR谱图；
图4：用4-(N,N-二甲基氨基)吡啶糖精盐作催化剂制备得到的聚戊内酯在体积排阻色谱分析中的谱图；
具体实施方式
通过下列实施例可以进一步说明本发明，实施例是为了说明而非限制本发明的。本领域的任何普通技术人员都能够理解这些实施例不以任何方式限制本发明，可以对其做适当的修改和数据变换而不违背本发明的实质和偏离本发明的范围。
实施例中所用的催化剂吡啶糖精盐结构式如式Ⅲ所示：
Figure PCTCN2018084185-appb-000012
实施例1
在10mL聚合管中，加入丁内酯(0.3856克，2.88毫摩尔)、苯甲醇(10微升，0.096毫摩尔)、编号13所示化合物(0.029g，0.096毫摩尔)，90℃磁力搅拌2h。反应结束后，所得粗产物溶于最少量的二氯甲烷，再加入冷的甲醇溶液中，有聚合物析出。离心分离得到白色 固体0.23g，转移至真空干燥箱中干燥。聚合物结构通过 1H NMR与 13C NMR鉴定，聚合物的分子量及分散度通过GPC测定。经测定，聚合物的转化率为90.6％，数均分子量M n为2600g mol -1,M n/M w为1.36。本发明所述编号13所示化合物，在250ml反应瓶中，加入编号1所示化合物(12.27mmol，1.5g)，糖精(12.27mmol，1.5g)，在四氢呋喃(THF)溶液中60℃搅拌过夜反应。在真空条件下除去溶剂，获得粗产物。加入甲醇(10ml)，己烷(20ml)重结晶，在室温下一段时间得到白色晶体。过滤干燥后使用。
实施例2
在10mL聚合管中，加入戊内酯(0.288克，2.88毫摩尔)、苯甲醇(10微升，0.096毫摩尔)，编号14所示化合物(0.0375g，0.096毫摩尔)，90℃磁力搅拌1h。反应结束后，所得粗产物溶于最少量的二氯甲烷，再加入冷的甲醇溶液中，有聚合物析出。离心分离得到白色固体0.21g，转移至真空干燥箱中干燥。聚合物结构通过 1H NMR与 13C NMR鉴定，聚合物的分子量及分散度通过GPC测定。经测定，聚合物的转化率为92.8％，数均分子量M n为2900g mol -1,M n/M w为1.21。本发明所述编号14所示化合物，在250ml反应瓶中，加入编号2所示化合物(12.27mmol，1.5g)，糖精(12.27mmol，1.5g)，在四氢呋喃(THF)溶液中60℃搅拌过夜反应。在真空条件下除去溶剂，获得粗产物。加入甲醇(10ml)，己烷(20ml)重结晶，在室温下一段时间得到白色晶体。过滤干燥后使用。
实施例3
在10mL聚合管中，加入己内酯(0.328克，2.88毫摩尔)、苯甲醇(10微升，0.096毫摩尔)、编号16所示化合物(0.038g，0.096毫摩尔)，100℃磁力搅拌1h。反应结束后，所得粗产物溶于最少量的二氯甲烷，再加入冷的甲醇溶液中，有聚合物析出。离心分离得到白色固体0.23g，转移至真空干燥箱中干燥。聚合物结构通过 1H NMR与 13C NMR鉴定，聚合物的分子量及分散度通过GPC测定。经测定，聚合物的转化率为98.7％，数均分子量M n为3500g mol -1，M n/M w为1.37。本发明所述编号16所示化合物，在250ml反应瓶中，加入编号4所示化合物(12.27mmol，1.5g)，糖精(12.27mmol，1.5g)，在四氢呋喃(THF)溶液中60℃搅拌过夜反应。在真空条件下除去溶剂，获得粗产物。加入甲醇(10ml)，己烷(20ml)重结晶，在室温下一段时间得到白色晶体。过滤干燥后使用。
实施例4
在10mL聚合管中，加入乙交酯(0.6682克，5.76毫摩尔)、苯甲醇(10微升，0.096毫摩尔)、编号18所示化合物(0.032g，0.096毫摩尔)，140℃磁力搅拌3h。反应结束后，所得粗产物溶于最少量的二氯甲烷，再加入冷的甲醇溶液中，有聚合物析出。离心分离得到白色固体0.47g，转移至真空干燥箱中干燥。聚合物结构通过 1H NMR与 13C NMR鉴定，聚合物的分子量及分散度通过GPC测定。经测定，聚合物的转化率为92.9％，数均分子量M n为6600g mol -1，M n/M w为1.24。本发明所述编号18所示化合物，在250ml反应瓶中，加入编号6所示化合物(12.27mmol，1.5g)，糖精(12.27mmol，1.5g)， 在四氢呋喃(THF)溶液中60℃搅拌过夜反应。在真空条件下除去溶剂，获得粗产物。加入甲醇(10ml)，己烷(20ml)重结晶，在室温下一段时间得到白色晶体。过滤干燥后使用。
实施例5
在10mL聚合管中，加入丙交酯(1.2441克，8.64毫摩尔)、苯甲醇(10微升，0.096毫摩尔)、编号19所示化合物(0.036g，0.096毫摩尔)，140℃磁力搅拌5h。反应结束后，所得粗产物溶于最少量的二氯甲烷，再加入冷的甲醇溶液中，有聚合物析出。离心分离得到白色固体0.87g，转移至真空干燥箱中干燥。聚合物结构通过 1H NMR与 13C NMR鉴定，聚合物的分子量及分散度通过GPC测定。经测定，聚合物的转化率为93.4％，数均分子量M n为12100g mol -1，M n/M w为1.36。本发明所述编号19所示化合物，在250ml反应瓶中，加入编号7所示化合物(12.27mmol，1.5g)，糖精(12.27mmol，1.5g)，在四氢呋喃(THF)溶液中60℃搅拌过夜反应。在真空条件下除去溶剂，获得粗产物。加入甲醇(10ml)，己烷(20ml)重结晶，在室温下一段时间得到白色晶体。过滤干燥后使用。
实施例6
在10mL聚合管中，加入溴代乙交酯(0.794克，2.88毫摩尔)、苯甲醇(10微升，0.096毫摩尔)、编号21所示化合物(0.029g，0.096毫摩尔)，140℃磁力搅拌3h。反应结束后，所得粗产物溶于最少量的二氯甲烷，再加入冷的甲醇溶液中，有聚合物析出。离心分离得到白色固体0.56g，转移至真空干燥箱中干燥。聚合物结构通过 1H NMR 与 13C NMR鉴定，聚合物的分子量及分散度通过GPC测定。经测定，聚合物的转化率为93.4％，数均分子量M n为7700g mol -1，M n/M w为1.25。本发明所述编号21所示化合物，在250ml反应瓶中，加入编号9所示化合物(12.27mmol，1.5g)，糖精(12.27mmol，1.5g)，在四氢呋喃(THF)溶液中60℃搅拌过夜反应。在真空条件下除去溶剂，获得粗产物。加入甲醇(10ml)，己烷(20ml)重结晶，在室温下一段时间得到白色晶体。过滤干燥后使用。
实施例7
在10mL聚合管中，加入丁交酯(0.4953克，2.88毫摩尔)、苯甲醇(10微升，0.096毫摩尔)、编号22所示化合物(0.025g，0.096毫摩尔)，150℃磁力搅拌10h。反应结束后，所得粗产物溶于最少量的二氯甲烷，再加入冷的甲醇溶液中，有聚合物析出。离心分离得到白色固体0.35g，转移至真空干燥箱中干燥。聚合物结构通过 1H NMR与 13C NMR鉴定，聚合物的分子量及分散度通过GPC测定。经测定，聚合物的转化率为95.4％，数均分子量M n为5100g mol -1，M n/M w为1.28。本发明所述编号22所示化合物，在250ml反应瓶中，加入编号10所示化合物(12.27mmol，1.5g)，糖精(12.27mmol，1.5g)，在四氢呋喃(THF)溶液中60℃搅拌过夜反应。在真空条件下除去溶剂，获得粗产物。加入甲醇(10ml)，己烷(20ml)重结晶，在室温下一段时间得到白色晶体。过滤干燥后使用。
实施例8
在10mL聚合管中，加入O-羧酸内酸酐(0.4147g，5.76毫摩尔)、 苯甲醇(10微升，0.096毫摩尔)、编号18所示化合物(0.036g，0.096毫摩尔)，130℃磁力搅拌5h。反应结束后，所得粗产物溶于最少量的二氯甲烷，再加入冷的甲醇溶液中，有聚合物析出。离心分离得到白色固体0.29g，转移至真空干燥箱中干燥。聚合物结构通过 1H NMR与 13C NMR鉴定，聚合物的分子量及分散度通过GPC测定。经测定，聚合物的转化率为96.3％，数均分子量M n为4300g mol -1，M n/M w为1.27。本发明所述编号18所示化合物，在250ml反应瓶中，加入编号6所示化合物(12.27mmol，1.5g)，糖精(12.27mmol，1.5g)，在四氢呋喃(THF)溶液中60℃搅拌过夜反应。在真空条件下除去溶剂，获得粗产物。加入甲醇(10ml)，己烷(20ml)重结晶，在室温下一段时间得到白色晶体。过滤干燥后使用。
实施例9
在10mL聚合管中，加入丙交酯(0.4147g，2.88毫摩尔)、苯甲醇(10微升，0.096毫摩尔)、编号13所示化合物(0.029g，0.096毫摩尔)，120℃磁力搅拌4h。反应结束后，所得粗产物溶于最少量的二氯甲烷，再加入冷的甲醇溶液中，有聚合物析出。离心分离得到白色固体0.28g，转移至真空干燥箱中干燥。聚合物结构通过 1H NMR与 13C NMR鉴定，聚合物的分子量及分散度通过GPC测定。经测定，聚合物的转化率为98.4％，数均分子量M n为4400g mol -1，M n/M w为1.13。本发明所述编号13所示化合物，在250ml反应瓶中，加入编号1所示化合物(12.27mmol，1.5g)，糖精(12.27mmol，1.5g)，在四氢呋喃(THF)溶液中60℃搅拌过夜反应。在真空条件下除去 溶剂，获得粗产物。加入甲醇(10ml)，己烷(20ml)重结晶，在室温下一段时间得到白色晶体。过滤干燥后使用。
实施例10
在10mL聚合管中，加入丙交酯(0.4147g，2.88毫摩尔)、苯甲醇(10微升，0.096毫摩尔)、编号13所示化合物(0.029g，0.096毫摩尔)，150℃磁力搅拌2h。反应结束后，所得粗产物溶于最少量的二氯甲烷，再加入冷的甲醇溶液中，有聚合物析出。离心分离得到白色固体0.29g，转移至真空干燥箱中干燥。聚合物结构通过 1H NMR与 13C NMR鉴定，聚合物的分子量及分散度通过GPC测定。经测定，聚合物的转化率为96.4％，数均分子量M n为4400g mol -1，M n/M w为1.29。本发明所述编号13所示化合物，在250ml反应瓶中，加入编号1所示化合物(12.27mmol，1.5g)，糖精(12.27mmol，1.5g)，在四氢呋喃(THF)溶液中60℃搅拌过夜反应。在真空条件下除去溶剂，获得粗产物。加入甲醇(10ml)，己烷(20ml)重结晶，在室温下一段时间得到白色晶体。过滤干燥后使用。

Claims (10)

  1. 一种聚酯的制备方法，其特征在于：引发剂醇引发环状内酯单体或环状碳酸酯单体的开环，在如式Ⅰ所示的糖精和如式Ⅱ所示的取代吡啶环制备得到如式III所示的吡啶糖精盐催化下引发小分子单体的开环聚合，得到聚酯；
    Figure PCTCN2018084185-appb-100001
    所述的糖精如式Ⅰ所示，取代吡啶环如式Ⅱ所示，其中R 1，R 2，R 3选自N,N二甲基氨基，吡咯烷基，氢，具有1～10个碳原子的烷基，具有1～10个碳原子的烷基并被卤原子、羟基、苯基或取代苯基中的一种或多种相同或不同基团所取代。
  2. 根据权利要求1所述的制备方法，其特征在于：式Ⅱ中，当R 1选自N,N-二甲基氨基，吡咯烷基，氢中的一种，R 2、R 3可分别选自为氢，乙基，异丙基，叔丁基或仲丁基中的相同或不同基团；或者是具有1～10个碳原子并被卤原子、羟基，苯基和取代苯基中相同或不同基团；
    当R 3选自N,N-二甲基氨基，吡咯烷基，氢中的一种，R1、R 2可分别选自氢，乙基，异丙基，叔丁基或仲丁基中的相同或不同基 团；或者是具有1～10个碳原子并被卤原子、羟基，苯基和取代苯基中相同或不同基团。
  3. 根据权利要求2所述的制备方法，其特征在于：如式Ⅱ所示的取代吡啶环如编号1-12所示的结构
    Figure PCTCN2018084185-appb-100002
  4. 根据权利要求1所述的制备方法，其特征在于：所述的如式III所示的吡啶糖精盐催化剂由如式Ⅰ所示的糖精和如式Ⅱ所示的取代吡啶环在60℃的四氢呋喃溶液中过夜重结晶得到。
  5. 根据权利要求1所述的制备方法，其特征在于：所述的单体选自以下一种：
    (1)
    Figure PCTCN2018084185-appb-100003
    其中，A为[—(CR 1R 2)—] n，n为2-10的整数；R 1、R 2选自H、具有1-5个碳原子的烷基、具有1-5个碳原子并被卤原子或羟基取代的烷基，R 1、R 2选自相同或不相同基团；X选自O或NH；
    (2)
    Figure PCTCN2018084185-appb-100004
    其中，A、B为[—(CR 1R 2)—] n，n为0-10的整数，A和B相同或不同；R 1、R 2选自H、具有1-5个碳原子的烷基、具有1-5个碳原子并被卤原子或羟基取代的烷基，R 1、R 2选自相同或不相同基团；X选自O或NH；
    (3)三亚甲基碳酸酯以及如式(VI)所示的的环状碳酸酯
    Figure PCTCN2018084185-appb-100005
    其中，R 1、R 2选自H、具有1～5个碳原子并被卤原子或羟基取代的烷基，R 1、R 2选自相同或不相同基团。
  6. 根据权利要求5所述的制备方法，其特征在于:所述的环状单体如式(IV)所示
    Figure PCTCN2018084185-appb-100006
    其中，A为[—(CR 1R 2)—] n
    当n＝2，R 1、R 2选自H，X选自O，环状单体为β-丙内酯；
    当n＝3，R 1、R 2选自H，X选自O，环状单体为γ-丁内酯；
    当n＝4，R 1、R 2选自H，X选自O，环状单体为δ-戊内酯；
    当n＝5，R 1、R 2选自H，X选自O，环状单体为ε-己内酯；
    当n＝10，R 1、R 2选自H，X选自O，环状单体为大环十一内酯；
    当n＝2，R 1、R 2选自H，X选自NH，环状单体为β-丙内酰胺；
    当n＝5，R 1、R 2选自H，X选自NH，环状单体为ε-己内酰胺；
    当n＝5，R 1选自氯原子，R 2选自H或R 1选自H，R 2选自氯原子，
    X选自O，环状单体为氯代己内酯。
  7. 根据权利要5所述的制备方法，其特征在于，所述的环状单体如式(V)所示
    Figure PCTCN2018084185-appb-100007
    其中，A、B为[—(CR 1R 2)—] n
    当n＝1，A和B相同，R 1、R 2选自H，X选自O，环状单体为乙交酯；
    当n＝1，A和B相同，R 1选自甲基，R 2选自H或R 1选自H，R 2选自甲基，X选自O，环状单体为丙交酯；
    当n＝1，A和B相同，R 1选自溴，R 2选自H或R 1选自H，R 2选自溴，X选自O，环状单体为溴代乙交酯；
    当n＝1，A和B相同，R 1选自甲基，R 2选自H或R 1选自H，R 2选自甲基，X选自NH，环状单体为3,6-二甲基对氧氮己环-2,5-二酮；
    当n＝2，A和B相同，R 1选自甲基，R 2选自H或R 1选自H，R 2选自甲基，X选自O，环状单体为丁交酯；
    当n＝8，A和B相同，R 1选自甲基，R 2选自H或R 1选自H，R 2选自甲基，X选自O，环状单体为癸交酯；
    当n＝10，A和B相同，R 1选自甲基，R 2选自H或R 1选自H，R 2选自甲基，X选自O，环状单体为大环十交酯。
    当A和B不同，A中n＝1，B中n＝0，R 1、R 2选自H，X选自O，环状单体为O-羧酸内酸酐；
    当A和B不同，A中n＝1，B中n＝0，R 1、R 2选自H，X选自N，环状单体为N-羧酸内酸酐。
  8. 根据权利要求5所述的制备方法，其特征在于：所述的单体为三亚甲基碳酸酯、羟基三亚甲基碳酸酯、氯代三亚甲基碳酸酯。
  9. 根据权利要求1所述的制备方法，其特征在于：所述的引发剂醇 为甲醇，乙醇，正丙醇，异丙醇，正丁醇，叔丁醇，苯甲醇，苯乙醇，乙二醇，缩乙二醇或季戊四醇。
  10. 根据权利要求1所述的制备方法，其特征在于：所述的反应在本体聚合法，反应温度为90-150℃；所述的方法还包括将反应产物用良溶剂溶解后在溶剂中析出，所述的良溶剂为二氯甲烷、三氯甲烷、甲苯、苯、丙酮或四氢呋喃，所述的溶剂为甲醇，乙醇或水。
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