CN101891884A - Polyester polycondensation catalyst and preparation method and application thereof - Google Patents
Polyester polycondensation catalyst and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a polyester polycondensation catalyst and a preparation method and application thereof. The preparation method of the polyester polycondensation catalyst comprises the following steps of: reacting TiO2/SiO2 sol with a nitrogenous or phosphorous compound; and controlling the grain size of a product to obtain the polyester polycondensation catalyst. The preparation method of the polyester polycondensation catalyst has a simple and convenient process, is easy to operate and is suitable for large-scale industrial production; besides, the catalyst provided by the invention has high catalytic efficiency, not only can catalyze the polymerization of aromatic polyesters and co-polyesters thereof, but also can catalyze the polymerization of aliphatic polyesters and co-polyesters thereof by changing the proportions of components of the catalyst and adjusting and controlling the activity of the catalyst, and has extensive application prospects.
Description
Technical field
The present invention relates to a kind of polyester polycondensation catalyst and preparation method thereof and application.
Background technology
Polyester is a kind of very important material since it possessed preferably character such as mechanical property, heat and chemical stability and cost lower, be widely used in packing, traffic, weaving, building waits the field that is closely related with people's daily life.Now, China has become the first in the world macrocyclic polyester producing country, and domestic polyester output was above 2,000 ten thousand tons in 2007.
Though China's production of polyester is larger, the catalyzer that domestic polyester production device mainly uses is still the antimony-based catalyst that human body and environment is had genotoxic potential.Use the polyester material of antimony-based catalyst preparation, over-all properties is more stable, but because shortcomings such as the toxicity of antimony and product burnt hair, antimony-based catalyst has by Titanium series catalyst alternate trend.
Novel Titanium series catalyst has had many reports both at home and abroad, such as: Dutch Acordis company has developed the C94 Ti-Si catalyst that can be used for various polycondensation of polyester, and main component is TiO
2-SiO
2Mixture.Wherein Ti/Si content ratio is about 9: 1, and the C94 activity is very high, and its activity approximately is Sb when preparation PET
2O
35-10 doubly; U.S. Eastman Chemical applies for a Titanium series catalyst patent of invention in December, 1994, its technical characterictic is to adopt alkyl titanate and phosphorus compound, cobalt compound (Cobaltous diacetate), toning agent (anthraquinone class or ketone compounds) to form catalyst system, and catalytic activity is higher than 6.6 times of antimonous oxide at least; Japan Supreme Being people company is respectively at having applied for the Titanium series catalyst patent of invention in June, 1999, November and in February, 2000, its technical characterictic is to adopt titanic acid ester or have the titanic acid ester of low polymerization degree (2-3) and the titanium compound and long carbochain phosphinic acid compounds, organic Blues toner composition catalyst system of aromatic multi-carboxy acid or anhydride reaction generation, and catalyst levels and antimony-based catalyst are suitable substantially.Though these activity of such catalysts are higher than antimony-based catalyst, active lifting is also not obvious, and major cause may be that these catalyzer are mostly based on TiO
2, be a kind of different-phase catalyst, so catalyst particle size can influence activity.If can be by the particle diameter of certain means control catalyst, its activity must be further enhanced.In addition, at present the Titanium series catalyst of these reports almost without exception needs add cobalt compound or organic dye is mixed colours, and use P contained compound etc. as stablizer.This illustrates that these catalyzer well do not solve the Titanium series catalyst hyperactivity, can make the shortcoming of product jaundice; Simultaneously, the adding of these additives has increased cost to manufacturing enterprise, and the adding of these " impurity " also is unfavorable for serialization production.In addition, from the result of bibliographical information, the material colourity L value of these Preparation of Catalyst is not high, and brightness is not enough, need add expensive m-phthalic acid when polyester is used as wrapping material, has improved production cost greatly.
Except catalyst toxicity, another big problem that China PET produces is that the PET product mainly concentrates on low value-added short fiber and section, dog-eat-dog; And the higher PET engineering plastics slower development of price, the main products on the market still needs a large amount of imports.The major cause that causes PET to be difficult to directly to be applied in the engineering plastics aspect is that the PET crystallization velocity of non-modified is slow, and the shaping mould temperature is high, and molding cycle is long, can the generation sticking to mould in the course of processing and phenomenons such as warpage, have a strong impact on product property.And main solution is to add nucleator, crystallization promoter etc. by means such as blend to quicken the PET crystallization at present; The content that reduces polyester matrix middle-end carboxyl simultaneously improves the hydrolytic resistance of PET in the course of processing.But PET produces degraded owing to be subjected to the unavoidable meeting of the effect of hot oxygen in the blend process, thereby influences product property.If can improve the crystallization velocity of PET and reduce content of carboxyl end group by synthetic appropriate catalyst, will extremely help the research and development of PET engineering plastics.If can develop a kind of based on nano level TiO
2/ SiO
2The high reactivity polycondensation catalyst, and utilize the nucleogenesis of inorganic nanoparticles to improve the crystallization rate of PET, will obtain the effect of achieving many things at one stroke.
In sum, it is very necessary developing a kind of novel titanium polyester polycondensation catalyst.
Summary of the invention
The purpose of this invention is to provide a kind of polyester polycondensation catalyst and preparation method thereof and application.
The method for preparing polyester polycondensation catalyst provided by the invention is with TiO
2/ SiO
2Colloidal sol and nitrogenous or P contained compound reaction, and, obtain polyester polycondensation catalyst by certain drying purification means.
In this method, nitrogenous compound is the pyridine haloid, amino acid and the derivative thereof that replace of imidazoles haloid, pyridinium salt, C2-C18 alkyl that imidazole salts, C2-C18 alkyl replace (as omega-amino acid, a-amino acid, amino 12 acid of 12-and various based on amino acid whose derivative etc.), lactan and derivative thereof (as hexanolactam, spicy inner formyl amine and various derivatives based on lactan etc.), coupling agent (as silane coupling agent KH550, KH560, titante coupling agent etc.), polyvinylpyrrolidone or polyacrylamide; P contained compound is the haloid that triphenylphosphate, triphenyl phosphite, trimethyl phosphite 99, triphenyl phosphorus or C2-C18 alkyl replace triphenyl phosphorus.TiO
2Colloidal sol and SiO
2In the mixture of colloidal sol, the mol ratio of Ti and Si is 9: 1-1: 9, preferred 1: 1-1: 9; N in described Ti and the described nitrogenous compound or the mol ratio of the P in the described P contained compound are 4: 1-1: 10, preferred 1: 1-1: 8.Temperature of reaction is 0-80 ℃, and the reaction times is 30min-24hr.This reaction is carried out in solvent; Described solvent is selected from least a in water, methyl alcohol, ethanol, Virahol, benzene and homologue thereof, acetone and the tetrahydrofuran (THF).
In addition, used TiO in this method
2Colloidal sol is prepared as follows and obtains: with titanium-containing compound hydrolysis in water and/or alcoholic solution, obtain described TiO
2Colloidal sol;
SiO
2Colloidal sol is prepared as follows and obtains: with silicon-containing compound hydrolysis in water and/or alcoholic solution, obtain described SiO
2Colloidal sol.
Wherein, titanium-containing compound is the mixture of any one or its arbitrary proportion in titanous chloride, titanium tetrachloride, metatitanic acid four isobutyl esters, tetra-n-butyl titanate or the titanium sulfate; Described silicon-containing compound is the mixture of any one or its arbitrary proportion in tetraethoxy or the water glass; The pH value of described hydrolysis reaction system is 0-4.
By choosing different organism and TiO
2Effect also selects for use the different dry methods of purification can the control catalyst particle diameter.Utilize the particle diameter of the polyester polycondensation catalyst that method for preparing obtains to be 5nm～1000nm, be preferably 10～500nm.
In addition, polyester polycondensation catalyst and the application of this polyester polycondensation catalyst in preparation aromatic polyester or aliphatic polyester compound according to above-mentioned preparation method obtains also belong to protection scope of the present invention.Polyester polycondensation catalyst provided by the invention, suitable polyester comprises aromatic polyester or copolyesters; Wherein, aromatic polyester or copolyesters are the polycondensation product or the copolycondensation product of dioctyl phthalate or dioctyl phthalate dimethyl ester and dibasic alcohol; Described dioctyl phthalate is a terephthalic acid, 2,6-naphthalic acid, m-phthalic acid, Succinic Acid, carbonic acid, hexanodioic acid, P-hydroxybenzoic acid or 4,4 '-the xenyl dicarboxylic acid; Described dioctyl phthalate dimethyl ester is a dimethyl terephthalate (DMT), 2,6-naphthalene diformic acid dimethyl ester, dimethyl isophthalate, dimethyl succinate, methylcarbonate, dimethyl adipate, P-hydroxybenzoic acid dimethyl ester or 4,4 '-the xenyl dimethyl dicarboxylate; Described dibasic alcohol is an ethylene glycol, 1, and ammediol, 1,2-propylene glycol, 1,4-butyleneglycol, 1,4 cyclohexane dimethanol, glycol ether, molecular weight are lower than 2000 polyoxyethylene glycol or molecular weight and are lower than 3000 PTMG.Described aliphatic polyester compound is a butyleneglycol, 1,2-propylene glycol or 1, the polycondensation product of ammediol and Succinic Acid, dimethyl succinate, carbonic acid, methylcarbonate, hexanodioic acid or dimethyl adipate or copolycondensation product.
Utilize this method to prepare the gained catalyzer, can improve catalyst activity by regulating phosphorous or nitrogenous compound kind and reaction times, purification means are controlled the gained catalyst particle size.
The coordination of the phosphorous or nitrogenous compound by high thermal stability has improved the catalytic selectivity of Ti: improved activity of such catalysts (the molar weight activity in metallic element is more than 60 times of antimony-based catalyst) greatly; Simultaneously good restraining the generation of side reaction, end carboxyl, the glycol ether equal size of gained material are extremely low, brightness height, the shortcoming that has overcome general Titanium series catalyst of success.Simultaneously, the size of utilizing phosphorous or nitrogenous compound and purification means to regulate catalyst particle size, prepared nano level catalyzer, improve the active crystal property that utilizes nano level dispersive silicon-dioxide, titanium dioxide granule to improve product simultaneously (Tc is up to 220 ℃ during 20 ℃/min of prepared PET cooling), improve the processing characteristics of polyester, helped preparing the PET engineering plastics.The preparation method of preparation polyester polycondensation catalyst provided by the invention, technology is easy, easy handling, be suitable for large-scale industrial production, and catalyst efficient height provided by the present invention, can not only catalyze aromatic polyester and copolyesters polymerization thereof, also can be by changing the proportioning of catalyst component, the regulation and control catalyst activity, catalysis aliphatic polyester and copolyesters polymerization thereof have broad application prospects.
Description of drawings
Fig. 1 is the x-ray photoelectron power spectrum of catalyzer D.
Fig. 2 is the x-ray photoelectron power spectrum of catalyzer H.
Embodiment
The invention will be further described below in conjunction with specific embodiment, but the present invention is not limited to following examples.
Intrinsic viscosity and end carboxyl concentration are all measured as follows among the following embodiment:
Intrinsic viscosity (I.V.): for aromatic polyester, the 0.1250g polyester is dissolved in 25ml phenol/sym.-tetrachloroethane (1/1wt) mixed solvent, in 25 ℃ of measurements.For aliphatic polyester, the 0.1250g polyester is dissolved in the 25mL meta-cresol, in 25 ℃ of measurements.
End carboxyl concentration: small amount of polyester is dissolved in the phenylcarbinol, is indicator with the phenolsulfonphthalein, carries out acid base titration with the potassium hydroxide ethylene glycol solution of 0.01mol/L and records.
Glycol ether content gas Chromatographic Determination; Product fusing point, Tc are measured with DSC; Colourity L, b value are measured with chromatographic instrument.
Embodiment 1, preparation polyester polycondensation catalyst
Get the 5mL concentrated hydrochloric acid, 10mL ethanol mixes with 19.6g tetraethoxy (TEOS) under the room temperature, stirs 1 hour, obtains product A SiO
2Colloidal sol.
Room temperature is got the 2.5g tetrabutyl titanate and is mixed with the 10mL concentrated hydrochloric acid, stirs 1 hour under the room temperature, obtains product B TiO
2Colloidal sol.
With product A SiO
2Colloidal sol and product B TiO
2Colloidal sol mixes, and 50 ℃ were stirred 12 hours, and obtained product C TiO
2/ SiO
2Colloidal sol.
Under 80 ℃, with product C TiO
2/ SiO
2The colloidal sol vacuum drying obtains catalyzer D.
With product C TiO
2/ SiO
2The colloidal sol lyophilize obtains catalyzer E.
With product C TiO
2/ SiO
2Colloidal sol is packed into and is placed deionized water in the semi-permeable membranes, removes Cl
-, obtain catalyzer F.
With product C TiO
2/ SiO
2With the reaction of 0.3g hexanolactam, obtain catalyzer G.
With product C TiO
2/ SiO
2With 0.05g silane coupling agent KH550 reaction, obtain catalyzer H.
With product C TiO
2/ SiO
2With 0.25g 1-hexadecyl-3-methyl bromination imidazoles reaction, obtain catalyst I.
Embodiment 2, preparation polyester polycondensation catalyst
Get the 5mL concentrated hydrochloric acid, 10mL ethanol mixes with 19.6g tetraethoxy (TEOS) under the room temperature, stirs 1 hour, obtains product A SiO
2Colloidal sol.
Get 2.5g TiCl
4Under 0 ℃, be added dropwise among the 20ml EG, and feed exsiccant NH
3Gas, the Nelles method that provides according to following document earlier is prepared, but product is not hydrolyzed, and is to be carried on SiO again
2On the colloidal sol: Li Dacheng, Zhou Dali, Chen Chaozhen, etc.The titanium ethylate synthesizes and hydrolysis prepares TiO
2The research of micro mist [J]. functional materials, 1995,26 (3): 278-282.
In above-mentioned preparation process, rapidly products therefrom is added among the A, obtain TiO
2/ SiO
2Colloidal sol J.
With lyophilize under the J vacuum condition, obtain catalyzer K.
J is handled with hydrothermal reaction at low temperature, hydrothermal temperature 50-200 ℃, 1-144 hour hydro-thermal time, obtain being numbered the polyester polycondensation catalyst of L.
The 1.69g triphenylphosphate is added among the colloidal sol J, and lyophilize obtains catalyzer M.
With catalyzer D and catalyzer K is example has been measured Ti with the x-ray photoelectron power spectrum electron binding energy.The x-ray photoelectron power spectrum found that (catalyzer D) when not adding organism Ti as depicted in figs. 1 and 2
2pElectron binding energy be 459.8eV.And after adding KH550 (catalyzer H), Ti
2pElectron binding energy be reduced to 457.8eV.TiO has been mentioned in the front
2Particle is to be carried on SiO
2Particle surface, therefore illustrate nitrogenous or phosphorus-containing matter is covered in TiO
2/ SiO
2Sol particle surface also forms coordination with Ti.
Measure the catalyst particle size that embodiment 1 prepares, the result is as shown in table 1.Data show, introduce organic constituent and in conjunction with the particle diameter that suitable drying purification means can control catalyst, help improving its activity.
The particle diameter of the catalyzer that table 1, embodiment 1 prepare
Measured the component of catalyzer D and catalyst I with electronics probe microscope (EPMA), the result shows that the mol ratio of Si and Ti is 12 among the catalyzer D, well meets with theoretical value (12.8); And the mol ratio 12.3 of Si and Ti in the catalyst I, organic content is 3.5wt%, equally very near theoretical value, illustrates that synthetic method that the present invention takes can be good at the ratio of each component of control catalyst.
Embodiment 3, polyester polycondensation catalyst in the preparation polyester material as Application of Catalyst
The step that the polyester polycondensation catalyst that utilizes the embodiment of the invention 1 to provide prepares the PET polyester material is as follows:
Get terephthalic acid 86.4g, ethylene glycol 32.3g is 0.3MPa at pressure, and temperature is to carry out esterification under 220-250 ℃ the condition, is steamed until the water of theoretical value.A kind of (catalyzer D-I) 1mg in the catalyzer that adding embodiment 1 prepares obtains PET material N-S respectively.Polycondensation time and product property are as shown in table 2.
From table 2 data as can be seen, the electron binding energy of titanium and the particle diameter of catalyzer affect activity of such catalysts greatly: for catalyzer D, E, F, particle diameter reduces successively, and activity increases, and product property also gets a promotion; And introducing nitrogenous compound and Ti carry out after the coordination, and activity further improves, and product property (specific performance) also far surpasses the product of antimony-based catalyst preparation.With the sample that the bigger catalyzer of particle diameter obtains, not only molecular weight is lower, and by-products contents such as end carboxyl, glycol ether are also higher, may be since polymerization time long due to.And with the PET material of the less Preparation of Catalyst of particle diameter, the molecular weight height, impurity in products is also less relatively.After introducing organism, organism can not only with the Ti coordination, suppress side reaction, more further control catalyst particle diameter.Products therefrom is foreign matter content low (product that end carboxyl, glycol ether content prepare far below antimony-based catalyst) not only, and because product P ET chain regularity makes the product fusing point up to 260 ℃ well, nano level TiO
2/ SiO
2Particle has also promoted the PET crystallization greatly, helps preparing the PET engineering plastics.
Table 2, with the fundamental property of the PET product of different catalysts preparation
Embodiment 4, the application of polyester polycondensation catalyst in the preparation polyester material
The step that the polyester polycondensation catalyst that utilizes the embodiment of the invention 2 to provide prepares the PBS polyester material is as follows:
Get butyleneglycol 115.1g, Succinic Acid 68.6g, place the reactor that feeds nitrogen, be warming up to 180 ℃ and carry out esterification, after the theoretical water gaging until 95% is steamed, a kind of 35mg among the catalyzer K-M that adding embodiment 2 prepares, at 180-240 ℃, pressure is lower than polycondensation 260min under the condition of 130Pa, obtains being numbered the poly-succinic fourth diester (PBS) of T-V, and reaction parameter sees Table 3.Can find out obviously equally that from table 3 the more little activity of catalyst particle size is high more, the product viscosity that within short polymerization time, obtains even higher with the catalyzer of small particle size.
Table 3, with the fundamental property of the PBS product of different catalysts preparation
Embodiment 5, the application of polyester polycondensation catalyst in the preparation polyester material
The step that the polyester polycondensation catalyst that utilizes the embodiment of the invention 2 to provide prepares the PPT polyester material is as follows:
Get dimethyl terephthalate (DMT) (DMT) 101.0g, 1,2-propylene glycol 79.2g, zinc acetate 0.03g, drop in the reactor of logical nitrogen together, be warming up to 200 ℃ and carry out transesterify, after the theoretical amount methyl alcohol until 95% is steamed, add the catalyzer M35mg that embodiment 2 prepares, at 250-290 ℃, pressure is lower than polycondensation 200min under the condition of 130Pa, obtains being numbered the poly terephthalic acid 1 of W, 2-propylene diester (PPT), intrinsic viscosity reaches 0.86.
Embodiment 6, the application of polyester polycondensation catalyst in the preparation polyester material
Get methylcarbonate 50g, 1,4-butyleneglycol 110g, add the catalyzer L 25mg that embodiment 2 prepares, drop in the reactor of logical nitrogen together, be warming up to 200 ℃ and carry out transesterify, the theoretical amount methyl alcohol until 95% is steamed the back and improves temperature to 240 ℃ and be lower than at pressure under the condition of 130Pa and carry out polycondensation, obtains molecular weight greater than 50,000 polyester material X.
The foregoing description explanation, after introducing different organism and Ti coordination, polyester polycondensation catalyst provided by the invention not only can be used for the synthetic of aromatic polyester, also can be used in the synthetic of aliphatic polyester, and activity is very high, even for transesterification reaction certain activity is arranged also.
Embodiment 7, comparative examples
Get dimethyl terephthalate (DMT) (DMT) 101.0g, ethylene glycol (EG) 71.0g, zinc acetate 0.02g drops in the reactor of logical nitrogen together, is warming up to 200 ℃ and carries out transesterification reaction, after the theoretical amount methyl alcohol until 95% is steamed, adds Sb
2O
330mg is at 260-290 ℃, and pressure is lower than polycondensation under the condition of 130Pa, obtains being numbered the PET material of Y, and data see Table 2.
As shown in Table 2, use antimony-based catalyst to prepare PET, polymerization time is 2 hours, but the catalyzer add-on is about 30 times of catalyzer H.Simultaneously, use Sb
2O
3The PET material Y various aspects of performance for preparing also is not so good as the PET material R of catalyzer H correspondence.Such as, PET material R has higher fusing point and Tc (fusing point is higher 6 ℃ than Y, and Tc is high 23 ℃); End carboxyl, glycol ether content is lower; Simultaneously R has better outward appearance, and its L value is up to 88, and can think also that by the b value phenomenon that Titanium series catalyst turns to be yellow PET also can ignore.
Claims (10)
1. a method for preparing polyester polycondensation catalyst is with TiO
2Colloidal sol and SiO
2The mixture of colloidal sol and nitrogenous or P contained compound react, and obtain described polyester polycondensation catalyst.
2. method according to claim 1 is characterized in that: described nitrogenous compound is selected from any one in pyridine haloid, amino acid, omega-amino acid, a-amino acid, 12 amino dodecanoic acid, lactan, hexanolactam, spicy inner formyl amine, silane coupling agent KH550, silane coupling agent KH560, titanate coupling agent, polyvinylpyrrolidone and the polyacrylamide that imidazoles haloid, pyridinium salt, C2-C18 alkyl that imidazole salts, C2-C18 alkyl replace replace;
Described P contained compound is the haloid that triphenylphosphate, triphenyl phosphite, trimethyl phosphite 99, triphenyl phosphorus or C2-C18 alkyl replace triphenyl phosphorus.
3. method according to claim 1 and 2 is characterized in that: described TiO
2Colloidal sol and SiO
2In the mixture of colloidal sol, the mol ratio of Ti and Si is 9: 1-1: 9, preferred 1: 1-1: 9; N in described Ti and the described nitrogenous compound or the mol ratio of the P in the described P contained compound are 4: 1-1: 10, preferred 1: 1-1: 8.
4. according to the arbitrary described method of claim 1-3, it is characterized in that: the temperature of described reaction is 0-80 ℃, and the time of reaction is 30 minutes-24 hours;
Described reaction is carried out in solvent; Described solvent is selected from least a in water, methyl alcohol, ethanol, Virahol, benzene and homologue thereof, acetone and the tetrahydrofuran (THF).
5. according to the arbitrary described method of claim 1-4, it is characterized in that: described TiO
2Colloidal sol is prepared as follows and obtains: with titanium-containing compound hydrolysis in water and/or alcoholic solution, obtain described TiO
2Colloidal sol;
Described SiO
2Colloidal sol is prepared as follows and obtains: with silicon-containing compound hydrolysis in water and/or alcoholic solution, obtain described SiO
2Colloidal sol.
6. method according to claim 5 is characterized in that: described titanium-containing compound is selected from least a in titanous chloride, titanium tetrachloride, metatitanic acid four isobutyl esters, tetra-n-butyl titanate and the titanium sulfate;
Described silicon-containing compound is selected from least a in tetraethoxy and the water glass;
The pH value of described hydrolysis reaction system is 0-4.
7. the polyester polycondensation catalyst that obtains of the arbitrary described preparation method of claim 1-6.
8. catalyzer according to claim 7 is characterized in that: the particle diameter of described catalyzer is 5nm～1000nm, preferred 10～500nm.
9. the application of the described polyester polycondensation catalyst of claim 7 in preparation aromatic polyester, aromatic copolyester or aliphatic polyester compound.
10. application according to claim 9 is characterized in that: described aromatic polyester or copolyesters are the polycondensation product or the copolycondensation product of dioctyl phthalate or dioctyl phthalate dimethyl ester and dibasic alcohol;
Described dioctyl phthalate is a terephthalic acid, 2,6-naphthalic acid, m-phthalic acid, Succinic Acid, carbonic acid, hexanodioic acid, P-hydroxybenzoic acid or 4,4 '-the xenyl dicarboxylic acid;
Described dioctyl phthalate dimethyl ester is a dimethyl terephthalate (DMT), 2,6-naphthalene diformic acid dimethyl ester, dimethyl isophthalate, dimethyl succinate, methylcarbonate, dimethyl adipate, P-hydroxybenzoic acid dimethyl ester or 4,4 '-the xenyl dimethyl dicarboxylate;
Described dibasic alcohol is an ethylene glycol, 1, and ammediol, 1,2-propylene glycol, 1,4-butyleneglycol, 1,4 cyclohexane dimethanol, glycol ether, molecular weight are lower than 2000 polyoxyethylene glycol or molecular weight and are lower than 3000 PTMG;
Described aliphatic polyester compound is a butyleneglycol, 1,2-propylene glycol or 1, the polycondensation product of ammediol and Succinic Acid, dimethyl succinate, carbonic acid, methylcarbonate, hexanodioic acid or dimethyl adipate or copolycondensation product.
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