CN103788379A - Modified polyethylene glycol succinate and preparation methods thereof - Google Patents
Modified polyethylene glycol succinate and preparation methods thereof Download PDFInfo
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- CN103788379A CN103788379A CN201210421284.2A CN201210421284A CN103788379A CN 103788379 A CN103788379 A CN 103788379A CN 201210421284 A CN201210421284 A CN 201210421284A CN 103788379 A CN103788379 A CN 103788379A
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Abstract
The invention relates to a toughening modification method of polyethylene glycol succinate. The method comprises a step that aliphatic polyester contacts and reacts with a hyperbranched polymer, the aliphatic polyester contains polyethylene glycol succinate, and the hyperbranched polymer is a product obtained through a polycondensation reaction of 2,2-dimethylol propionic acid and polyol having at least three alcoholic hydroxyl groups. The invention also relates to another toughening modification method of polyethylene glycol succinate. The another toughening modification method comprises the following steps: carrying out a polycondensation reaction of succinic acid and glycol, and carrying out a contact reaction of the above obtained polycondensation reaction product and the hyperbranched polymer, and the hyperbranched polymer is a product obtained through a polycondensation reaction of 2,2-dimethylol propionic acid and polyol having at least three alcoholic hydroxyl groups. The invention also relates to modified polyethylene glycol succinate prepared through the above methods. The modified polyethylene glycol succinate prepared through the methods has the advantages of good toughness and good biological degradability.
Description
Technical field
The present invention relates to a kind of toughening modifying method of polyethylene glycol succinate, and modification polyethylene glycol succinate obtained by this method.
Background technology
In recent years, aliphatic polyester has become a very important integral part in biodegradable plastic, as poly butyric ester (PHB), poly(lactic acid) (PLA) and poly butylene succinate (PBS) etc.Wherein, poly-succinic ester series is the performance such as fusing point is higher, Heat stability is good, high comprehensive performance owing to having, and has been subject to many investigators' favor, has now become the main aliphatic polyester of one of suitability for industrialized production.It is reported, PBS is 2.68 ten thousand tons the market demand of 2006, just reaches 10.18 ten thousand tons by 2010.Expect 2015 and can reach 33.93 ten thousand tons, average growth rate per annum can reach 28.9%.The consumption of present Japanese PBS has accounted for 1/3 of biodegradable polymers, is mainly used in agricultural aquatic products, building goods, materials and equipments, packing bag, refuse bag etc.
Polyethylene glycol succinate (PES) is as the homologue of PBS, the same with PBS, in the middle of biodegradable aliphatic polyester, belong to and there is better mechanical property and a stable on heating class, and compare with PBS, biodegradability is better, and price is cheaper, also can accomplish complete bio-based, resource does not consume petroleum.
At present also few about the report of PES, yet there is no commercially produced product, it is relevant that this may also not reach the performance requriements of a kind of single product of preparation with the performance index of itself.But, cheap due to PES, cost is well below existing commercial biodegradable plastic (as poly(lactic acid), PBS etc.), therefore, if strengthen the research and development of the subsequent product to PES, as the aspects such as heat-resisting, water-fast, mechanical property are effectively improved, make its performance can be compared with conventional plastic, be the key that makes its mass market.The shortcoming of PES be mainly hard and crisp, toughness is poor, this has greatly limited its application, to such an extent as to also there is no now industrialization product.CN101628972A discloses a kind of preparation method of polyethylene glycol succinate, adopt solution polymerization to make estrodur performed polymer, then add vulcabond, binary acyl chlorides or dibasic acid anhydride chain extension, to prepare number-average molecular weight 55,000-81, the polyethylene glycol succinate between 000.But the modification of PES is not studied.
Summary of the invention
The object of the invention is in order to solve the problem that polyethylene glycol succinate is hard and crisp, toughness is poor the modification polyethylene glycol succinate that a kind of toughening modifying method of polyethylene glycol succinate is provided and is prepared by the method.
The invention provides a kind of toughening modifying method of polyethylene glycol succinate, the method comprises aliphatic polyester and hyperbranched polymer contact reacts, described aliphatic polyester contains polyethylene glycol succinate, described hyperbranched polymer is the polycondensation product of 2,2-dimethylol propionic acid and the polyvalent alcohol with at least three alcoholic extract hydroxyl groups.
The present invention also provides a kind of toughening modifying method of polyethylene glycol succinate, the method comprises: succinic acid and ethylene glycol are carried out to polycondensation, then will obtain polycondensation product and hyperbranched polymer contact reacts, described hyperbranched polymer is the polycondensation product of 2,2-dimethylol propionic acid and the polyvalent alcohol with at least three alcoholic extract hydroxyl groups.
The present invention also provides the modification of being prepared by aforesaid method polyethylene glycol succinate.
In the toughening modifying method of described polyethylene glycol succinate provided by the invention, by described hyperbranched polymer and polyethylene glycol succinate are reacted, with by covalently bound described hyperbranched polymer in polyethylene glycol succinate, thereby the performance characteristics of hyperbranched polymer is attached in polyethylene glycol succinate, the toughness that the modification polyethylene glycol succinate tool of so preparation is significantly improved, particularly, show the tensile strength and the elongation at break that significantly improve.
Other features and advantages of the present invention are described in detail the embodiment part subsequently.
Accompanying drawing explanation
Fig. 1 is that 2,2-dimethylol propionic acid (DMPA), with TriMethylolPropane(TMP) (TMP), the process that hyperbranched polymer is prepared in polycondensation occurs.
Embodiment
According to an aspect of the present invention, the toughening modifying method of described polyethylene glycol succinate comprises aliphatic polyester and hyperbranched polymer contact reacts, described aliphatic polyester contains polyethylene glycol succinate, described hyperbranched polymer is the polycondensation product of 2,2-dimethylol propionic acid and the polyvalent alcohol with at least three alcoholic extract hydroxyl groups.
In the present invention, be for hyperbranched polymer is connected with polyethylene glycol succinate by the form of covalent linkage by described aliphatic polyester and the catalytic object of described hyperbranched polymer.Therefore, the contact reacts process of described aliphatic polyester and described hyperbranched polymer can be implemented according to conventional method, as long as can make polyethylene glycol succinate and described hyperbranched polymer react, the two is linked together by covalent linkage., described aliphatic polyester and the catalytic process of described hyperbranched polymer are comprised: described aliphatic polyester is heated to melting, then by the aliphatic polyester of melting and described hyperbranched polymer contact reacts more preferably in embodiment in one.Melt temperature can be 120-200 ℃, is preferably 140-180 ℃, more preferably 150-170 ℃.In above-mentioned preferred implementation, in whole reaction process, without using solvent, thereby without reclaiming solvent, also reduced the risk that the finished product are polluted simultaneously.
In described method, the contact reacts of described aliphatic polyester and described hyperbranched polymer is preferably to carry out under the condition of (preferably below 90Pa) below 200Pa under inert atmosphere or in vacuum tightness.Described inert atmosphere can be provided by the gas (as conventional rare gas element and nitrogen etc.) not reacting with described aliphatic polyester and described hyperbranched polymer.In the present invention, vacuum tightness represents by absolute pressure.
In described method, the contact reacts of described aliphatic polyester and described hyperbranched polymer is the condensation reaction of carboxyl and hydroxyl, and therefore, described catalytic condition can suitably be selected in conventional condensation reaction condition.Under preferable case, described catalytic temperature is 120-240 ℃, more preferably 150-185 ℃; The described catalytic time is 0.1-10 hour, more preferably 0.5-4 hour.
In described method, there is no particular limitation for the consumption of described aliphatic polyester and described hyperbranched polymer.Under preferable case, with respect to the consumption of the polyethylene glycol succinate of 100 weight parts, the consumption of described hyperbranched polymer is 0.1-10 weight part, more preferably 0.5-3 weight part.
In described aliphatic polyester, take the integral molar quantity of described aliphatic polyester as benchmark, the content of polyethylene glycol succinate can be 50-100 % by mole, is preferably 75-100 % by mole.
In described aliphatic polyester, except polyethylene glycol succinate, can also contain the aliphatic polyester except polyethylene glycol succinate.Contain polyethylene glycol succinate and except the aliphatic polyester polyethylene glycol succinate at described aliphatic polyester, take the integral molar quantity of described aliphatic polyester as benchmark, the content of described aliphatic polyester except polyethylene glycol succinate can be 0.01-50 % by mole, is preferably 10-25 % by mole; The content of polyethylene glycol succinate can be 50-99.99 % by mole, is preferably 75-90 % by mole.
In the present invention, there is no particular limitation for described aliphatic polyester except polyethylene glycol succinate, it can be the aliphatic polyester of various routines, as the polycondensate of the dibasic alcohol of the di-carboxylic acid of C2-C12 and C2-C12 (except polyethylene glycol succinate), concrete, it can be for example poly-succinic hexylene glycol ester, poly-hexanodioic acid hexylene glycol ester, poly-sebacic acid hexylene glycol ester, poly butylene succinate, poly adipate succinic acid ester, polydiethylene glycol sebacate, poly-succinic propylene glycol ester, polypropylene adipate (PPA), poly-sebacic acid propylene glycol ester, polyethylene glycol adipate, polyethylene glycol sebacate.Under preferable case, described aliphatic polyester except polyethylene glycol succinate is at least one in poly butylene succinate, polydiethylene glycol sebacate, poly-succinic propylene glycol ester, poly-sebacic acid propylene glycol ester, polyethylene glycol adipate and polyethylene glycol sebacate, more preferably at least one in poly butylene succinate, poly-succinic propylene glycol ester, poly-sebacic acid propylene glycol ester, polydiethylene glycol sebacate and polyethylene glycol sebacate.
In the present invention, the number-average molecular weight of described aliphatic polyester except polyethylene glycol succinate can be 1000-120,000, be preferably 10,000-80, and 000, more preferably 20,000-50,000.The molecular weight distributing index of described aliphatic polyester except polyethylene glycol succinate can be 1-5, is preferably 1.0-2.5.In the present invention, the molecular weight distributing index of polymkeric substance records according to gel permeation chromatography (GPC).
In the present invention, the number-average molecular weight of polyethylene glycol succinate can be 1000-80,000, be preferably 5000-30,000.In the present invention, the number-average molecular weight of polymkeric substance records according to gel permeation chromatography (GPC).The molecular weight distributing index of polyethylene glycol succinate can be 1-5, is preferably 1.0-2.5.
In the present invention, described hyperbranched polymer is the polycondensation product of 2,2-dimethylol propionic acid (DMPA) and the polyvalent alcohol with at least three alcoholic extract hydroxyl groups.The number-average molecular weight of described hyperbranched polymer can be 500-3000, is preferably 800-2000.The polyvalent alcohol in the preferred case, with at least three alcoholic extract hydroxyl groups is at least one in TriMethylolPropane(TMP) (TMP), tetramethylolmethane and glycerol.Most preferably, described hyperbranched polymer is the polycondensation product of 2,2-dimethylol propionic acid and TriMethylolPropane(TMP).The polycondensation process of 2,2-dimethylol propionic acid and TriMethylolPropane(TMP) as shown in Figure 1.In Fig. 1, the ratio that DMPA and TMP are about 3:1 with mol ratio is carried out polycondensation, add the tosic acid of DMPA and TMP gross weight 0.3% as catalyzer, the detailed process of this polycondensation can comprise: first under inert atmosphere, at the temperature of 80-120 ℃, react 0.5-1 hour, but be under the vacuum condition below 200Pa in vacuum tightness, at the temperature of 120-150 ℃, react 3-5 hour, thereby make hyperbranched polymer HBPE-1; Then, the ratio that hyperbranched polymer HBPE-1 and DMPA are about 1:6 with mol ratio is carried out polycondensation, add the tosic acid of HBPE-1 and DMPA gross weight 0.3% as catalyzer, the detailed process of this polycondensation can comprise: first under inert atmosphere, at the temperature of 80-120 ℃, react 0.5-1 hour, then be under the vacuum condition below 200Pa in vacuum tightness, at the temperature of 120-150 ℃, react 3-5 hour, thereby make hyperbranched polymer HBPE-2; Afterwards, the ratio that hyperbranched polymer HBPE-2 and DMPA are about 1:12 with mol ratio is carried out polycondensation, add the tosic acid of HBPE-2 and DMPA gross weight 0.3% as catalyzer, the detailed process of this polycondensation can comprise: first under inert atmosphere, at the temperature of 80-120 ℃, react 0.5-1 hour, then be under the vacuum condition below 200Pa in vacuum tightness, at the temperature of 120-150 ℃, react 3-5 hour, thereby make hyperbranched polymer HBPE-3; Then, the ratio that hyperbranched polymer HBPE-3 and DMPA are about 1:24 with mol ratio is carried out polycondensation, add the tosic acid of HBPE-3 and DMPA gross weight 0.3% as catalyzer, the detailed process of this polycondensation can comprise: first under inert atmosphere, at the temperature of 80-120 ℃, react 0.5-1 hour, then be under the vacuum condition below 200Pa in vacuum tightness, at the temperature of 120-150 ℃, react 3-5 hour, thereby make hyperbranched polymer HBPE-4.In described method provided by the invention, hyperbranched polymer HBPE-1, hyperbranched polymer HBPE-2, hyperbranched polymer HBPE-3 and hyperbranched polymer HBPE-4 all can be used as hyperbranched polymer polyethylene glycol succinate are carried out to toughening modifying.
In described method, the contact reacts process of described aliphatic polyester and described hyperbranched polymer is preferably carried out under the existence of chainextender.The in the situation that of introducing chainextender in described contact reacts, the modification polyethylene glycol succinate of final preparation has the toughness of further improvement.
As long as owing to adding the chainextender of little amount can reach the effect of further toughening modifying, therefore there is no particular limitation for the consumption of described chainextender.In the preferred case, with respect to the consumption of the polyethylene glycol succinate of 100 weight parts, the consumption of described chainextender is 0.01-6 weight part, more preferably 0.1-2 weight part.
Described chainextender can be the conventional various chainextenders that use in this area, for example, can be at least one in vulcabond, binary acid amides, binary acyl chlorides, polyvalent alcohol, polycarboxylic acid and the organic compound with at least one alcoholic extract hydroxyl group and at least one carboxyl.Described vulcabond can be for example 2,4 toluene diisocyanate, 4,4 '-diphenylmethanediisocyanate, hexamethylene diisocyanate, 3,3 '-dimethyl diphenyl base-4,4 '-vulcabond etc.Described binary acid amides can be for example urea.Described binary acyl chlorides can be for example oxalyl chloride, Adipoyl Chloride, terephthalyl chloride etc.Described polyvalent alcohol can be for example glycerol, tetramethylolmethane, TriMethylolPropane(TMP), 2-methylol-1,3-PD, BT, Glycerol dimer, triglycerin, Polyglycerine etc.Described polycarboxylic acid can be for example FUMARIC ACID TECH GRADE, citric acid, maleic anhydride, malonic anhydride, Tetra hydro Phthalic anhydride, Succinic anhydried, 1,3,5-hexanaphthene tricarboxylic acid etc.The described organic compound with at least one alcoholic extract hydroxyl group and at least one carboxyl can be for example 2,2-dimethylol propionic acid, oxyacetic acid, 6 hydroxycaproic acid, P-hydroxybenzoic acid etc.
In one more preferably in embodiment, the toughening modifying method of described polyethylene glycol succinate comprises: the mixture of polyethylene glycol succinate and other aliphatic polyesters (also i.e. aliphatic polyester except polyethylene glycol succinate) is heated to 120-200 ℃, make the complete melting of this mixture, then in the mixture of melting, add described chainextender and described hyperbranched polymer, under inert atmosphere, 0.1-10 hour (being preferably 0.5-4 hour) of 120-240 ℃ (being preferably 150-185 ℃) reaction, thereby can obtain the modification polyethylene glycol succinate with excellent toughness.
According to another aspect of the present invention, the toughening modifying method of described polyethylene glycol succinate comprises: succinic acid and ethylene glycol are carried out to polycondensation, then will obtain polycondensation product and hyperbranched polymer contact reacts, described hyperbranched polymer is the polycondensation product of 2,2-dimethylol propionic acid and the polyvalent alcohol with at least three alcoholic extract hydroxyl groups.
In one embodiment, described method can also be included in succinic acid and ethylene glycol are carried out adding in the process of polycondensation aliphatic dibasic acid except succinic acid and/or the aliphatic dihydroxy alcohol except ethylene glycol.
In described method, the mol ratio of the consumption of succinic acid and ethylene glycol can be 1:1-1.5, is preferably 1:1.1-1.3.
In described method, described except the aliphatic dibasic acid succinic acid and/or described except the aliphatic dihydroxy alcohol ethylene glycol in the case of adding, comprising succinic acid can be 1:1-1.5 with comprising ethylene glycol in the mol ratio of total consumption (being the consumption sum of ethylene glycol and described aliphatic dihydroxy alcohol except ethylene glycol) of interior aliphatic dihydroxy alcohol at total consumption (being the consumption sum of succinic acid and described aliphatic dibasic acid except succinic acid) of interior aliphatic dibasic acid, be preferably 1:1.1-1.3.
In described method, in the polycondensation process of succinic acid and ethylene glycol, or in the polycondensation process after adding described aliphatic dibasic acid and/or described aliphatic dihydroxy alcohol except ethylene glycol except succinic acid, the condition of described polycondensation can suitably be selected in conventional polycondensation condition.Under preferable case, the condition of described polycondensation comprises: temperature of reaction is 120-240 ℃, is preferably 130-230 ℃; Reaction times is 0.1-10 hour, is preferably 1-10 hour.
Described aliphatic dibasic acid except succinic acid can be the aliphatic dibasic acid of C2-C12, is preferably the aliphatic dibasic acid of C5-C12.Concrete, described aliphatic dibasic acid except succinic acid can be for example hexanodioic acid, sebacic acid, bay diacid etc.
Described aliphatic dihydroxy alcohol except ethylene glycol can be the aliphatic dibasic acid of C3-C12, is preferably the aliphatic dibasic acid of C3-C8.Concrete, described aliphatic dihydroxy alcohol except ethylene glycol can be for example butyleneglycol, hexylene glycol, 1,3-PD, 1,2-PD etc.
Further preferably, described polycondensation comprises two stages, and first stage is that aliphatic dibasic acid (containing succinic acid) and aliphatic dihydroxy alcohol (containing ethylene glycol) are reacted to 0.1-8 hour (being preferably 1-8 hour) under inert atmosphere under 120-200 ℃ (being preferably 130-190 ℃); Subordinate phase is that the initial reaction product that the described first stage is obtained injects vacuum distillation apparatus, and is to react 0.1-8 hour under the condition (being preferably below 90Pa) below 200Pa at 200-240 ℃, vacuum tightness, further to carry out polycondensation.Described inert atmosphere can be provided by the gas (as conventional rare gas element and nitrogen etc.) not reacting with aliphatic dibasic acid and aliphatic dihydroxy alcohol.
Described polycondensation is carried out under the existence of catalyzer.Described catalyzer can be the conventional catalyzer using in this area, for example, can be tetrabutyl titanate, germanium dioxide, antimonous oxide, the positive butyl ester of germanic acid, isopropyl titanate, tosic acid etc.There is no particular limitation for the consumption of described catalyzer, adds with conventional catalyst levels.Under preferable case, with respect to the consumption of the succinic acid of 100 weight parts, the consumption of described catalyzer can be 0.01-1 weight part, is preferably 0.08-0.5 weight part.
In described method, the contact reacts of described polycondensation product and described hyperbranched polymer is preferably to carry out under the condition of (preferably below 90Pa) below 200Pa under inert atmosphere or in vacuum tightness.Described inert atmosphere can be provided by the gas (as conventional rare gas element and nitrogen etc.) not reacting with described polycondensation product and described hyperbranched polymer.
In described method, the contact reacts of described polycondensation product and described hyperbranched polymer is the condensation reaction of carboxyl and hydroxyl, and therefore, described catalytic condition can suitably be selected in conventional condensation reaction condition.Under preferable case, described catalytic temperature is 200-240 ℃, and the described catalytic time is 0.1-10 hour.
In described method, there is no particular limitation for the consumption of described hyperbranched polymer.Under preferable case, with respect to the consumption of the succinic acid of 100 weight parts, the consumption of described hyperbranched polymer is 0.1-10 weight part, is preferably 0.5-3 weight part.
In described method, the contact reacts process of described polycondensation product and described hyperbranched polymer is preferably carried out under the existence of chainextender.The in the situation that of introducing chainextender in described contact reacts, the modification polyethylene glycol succinate of final preparation has the toughness of further improvement.
As long as owing to adding the chainextender of little amount can reach the effect of further toughening modifying, therefore there is no particular limitation for the consumption of described chainextender.In the preferred case, with respect to the consumption of the succinic acid of 100 weight parts, the consumption of described chainextender is 0.01-6 weight part, more preferably 0.1-2 weight part.
In aforesaid method, described hyperbranched polymer and described chainextender all with above describe identical.
In one more preferably in embodiment, the toughening modifying method of described polyethylene glycol succinate comprises: succinic acid and ethylene glycol are mixed, under inert atmosphere, 0.1-8 hour (being preferably 1-8 hour) of 120-200 ℃ (being preferably 130-190 ℃) lower reaction, steam until no longer include small molecules cut; Then, the polycondensation product obtaining is injected to vacuum distillation apparatus, be under the condition (being preferably below 90Pa) below 200Pa, to react 0.1-8 hour (being preferably 2-6 hour) in 200-240 ℃ (being preferably 200-230 ℃), vacuum tightness, then only add described hyperbranched polymer, or add described hyperbranched polymer and described chainextender simultaneously, and continue reaction 0.5-4 hour, thereby can obtain the modification polyethylene glycol succinate with excellent toughness.
At another kind more preferably in embodiment, the toughening modifying method of described polyethylene glycol succinate comprises: succinic acid and ethylene glycol are mixed, under inert atmosphere, 0.1-5 hour (being preferably 1-5 hour) of 120-180 ℃ (being preferably 130-160 ℃) lower reaction, steam until no longer include small molecules cut; Then, add other aliphatic dibasic acid (also i.e. aliphatic dibasic acid except succinic acid) and/or other aliphatic dihydroxy alcohol (also i.e. aliphatic dihydroxy alcohol except ethylene glycol), under inert atmosphere, 0.1-5 hour (being preferably 1-5 hour) of 140-200 ℃ (being preferably 140-180 ℃) lower reaction, steam until no longer include small molecules cut; Then, the polycondensation product obtaining is injected to vacuum distillation apparatus, be under the condition (being preferably below 90Pa) below 200Pa, to react 0.1-8 hour (being preferably 2-6 hour) in 200-240 ℃ (being preferably 200-230 ℃), vacuum tightness, then only add described hyperbranched polymer, or add described hyperbranched polymer and described chainextender simultaneously, and continue reaction 0.5-4 hour, thereby can obtain the modification polyethylene glycol succinate with excellent toughness.
The present invention also provides the modification of being prepared by aforesaid method polyethylene glycol succinate.The toughness that described modification polyethylene glycol succinate tool has clear improvement.Particularly, the elongation at break of polyethylene glycol succinate (PES) is only 1-20% conventionally, and the elongation at break of modification polyethylene glycol succinate prepared by aforesaid method according to the present invention can, up to more than 150%, be generally 150-1500%.
The invention will be further described by the following examples.
The present embodiment is for specification sheets described modification polyethylene glycol succinate provided by the invention and preparation method thereof.
Succinic acid and ethylene glycol are joined in there-necked flask take mol ratio as 1:1.3, then add the tetrabutyl titanate of 0.08 weight part (with respect to the succinic acid of 100 weight parts), under nitrogen atmosphere, be warming up to gradually 170 ℃ afterwards, react 4 hours, steam until no longer include small molecules cut; Then, the reaction product obtaining is injected to vacuum distillation apparatus, be warmed up to 220 ℃, the vacuum tightness of regulation system is for being less than 90Pa gradually, react after 4 hours, adding wherein the glycerol of 0.5 weight part (with respect to the succinic acid of 100 weight parts) and the hyperbranched polymer HBPE-3(number-average molecular weight of 0.5 weight part (with respect to the succinic acid of 100 weight parts) is 1300), temperature of reaction control is approximately 170 ℃, react 2 hours, obtain modification polyethylene glycol succinate A1.
Comparative example 1
Prepare modification polyethylene glycol succinate according to the method for embodiment 1, difference is not add described hyperbranched polymer HBPE-3, thereby make modification polyethylene glycol succinate D1.
The present embodiment is for specification sheets described modification polyethylene glycol succinate provided by the invention and preparation method thereof.
Succinic acid and ethylene glycol are joined in there-necked flask take mol ratio as 0.9:1.3, then add the tetrabutyl titanate of 0.1 weight part (with respect to the succinic acid of 100 weight parts), under nitrogen atmosphere, be warming up to gradually 160 ℃ afterwards, react 3 hours, steam until no longer include small molecules cut; Then the sebacic acid (with respect to the succinic acid of 1 molar part) that adds wherein 0.1 molar part, is warming up to 180 ℃, reacts 2 hours, steams until no longer include small molecules cut; Then, the reaction product obtaining is injected to vacuum distillation apparatus, be warmed up to 220 ℃, regulation system vacuum tightness is≤90Pa gradually, reacts 4 hours; Adding wherein the hyperbranched polymer HBPE-4(number-average molecular weight of 1.5 weight parts (with respect to the succinic acid of 100 weight parts) is 1600 again), temperature of reaction control is approximately 170 ℃, reacts 1 hour, obtains modification polyethylene glycol succinate A2.
The present embodiment is for specification sheets described modification polyethylene glycol succinate provided by the invention and preparation method thereof.
By succinic acid, ethylene glycol and 1,2-propylene glycol joins in there-necked flask take mol ratio as 1:1.1:0.2, then add the tetrabutyl titanate of 0.1 weight part (with respect to the succinic acid of 100 weight parts), under nitrogen atmosphere, be warming up to gradually 150 ℃ afterwards, react 4 hours, steam until no longer include small molecules cut; Then, the reaction product obtaining is injected to vacuum distillation apparatus, be warmed up to 230 ℃, regulation system vacuum tightness is≤90Pa gradually, reacts 4 hours; Adding wherein the hyperbranched polymer HBPE-4(number-average molecular weight of 1.0 weight parts (with respect to the succinic acid of 100 weight parts) is 1600 again), temperature of reaction control is approximately 185 ℃, reacts 1 hour, obtains modification polyethylene glycol succinate A3.
The present embodiment is for specification sheets described modification polyethylene glycol succinate provided by the invention and preparation method thereof.
Prepare modification polyethylene glycol succinate according to the method for embodiment 3, difference is, in adding hyperbranched polymer HBPE-4, add the TriMethylolPropane(TMP) of 1.5 weight parts (with respect to the succinic acid of 100 weight parts), thereby make modification polyethylene glycol succinate A4.
Embodiment 5
The present embodiment is for specification sheets described modification polyethylene glycol succinate provided by the invention and preparation method thereof.
By polyethylene glycol succinate, (number-average molecular weight is 6640, molecular weight distributing index is 1.7) and polyethylene glycol sebacate (number-average molecular weight is 33000, molecular weight distributing index is 1.9) join in there-necked flask take mol ratio as 3:1, under nitrogen atmosphere, be warming up to gradually 155 ℃ afterwards, after treating complete melting, under agitation add 4 of 0.5 weight part (with respect to the PES of 100 weight parts), the hyperbranched polymer HBPE-3(number-average molecular weight of 4 '-diphenylmethanediisocyanate and 2.0 weight parts (with respect to the PES of 100 weight parts) is 1300), temperature of reaction control is approximately 150 ℃, react 1 hour, obtain modification polyethylene glycol succinate A5.
Embodiment 6
The present embodiment is for specification sheets described modification polyethylene glycol succinate provided by the invention and preparation method thereof.
Prepare modification polyethylene glycol succinate according to the method for embodiment 5, difference is, with the hyperbranched polymer HBPE-4(number-average molecular weight of identical weight be 1600) replace described hyperbranched polymer HBPE-3, thereby make modification polyethylene glycol succinate A6.
Embodiment 7
The present embodiment is for specification sheets described modification polyethylene glycol succinate provided by the invention and preparation method thereof.
By polyethylene glycol succinate, (number-average molecular weight is 12000, molecular weight distributing index is 1.8) and poly butylene succinate (number-average molecular weight is 43000, molecular weight distributing index is 1.7) join in there-necked flask take mol ratio as 4:1, under nitrogen atmosphere, be warming up to gradually 165 ℃ afterwards, after treating complete melting, under agitation adding the hexamethylene diisocyanate of 1.5 weight parts (with respect to the PES of 100 weight parts) and the hyperbranched polymer HBPE-4(number-average molecular weight of 2.0 weight parts (with respect to the PES of 100 weight parts) is 1600), temperature of reaction control is approximately 170 ℃, react 0.5 hour, obtain modification polyethylene glycol succinate A7.
Embodiment 8
The present embodiment is for specification sheets described modification polyethylene glycol succinate provided by the invention and preparation method thereof.
By polyethylene glycol succinate, (number-average molecular weight is 12000, molecular weight distributing index is 1.8) and polyethylene glycol sebacate (number-average molecular weight is 33000, molecular weight distributing index is 1.9) join in there-necked flask take mol ratio as 9:1, under nitrogen atmosphere, be warming up to gradually 155 ℃ afterwards, after treating complete melting, under agitation adding the hexamethylene diisocyanate of 1.5 weight parts (with respect to the PES of 100 weight parts) and the hyperbranched polymer HBPE-4(number-average molecular weight of 2.0 weight parts (with respect to the PES of 100 weight parts) is 1600), temperature of reaction control is approximately 160 ℃, react 1 hour, obtain modification polyethylene glycol succinate A8.
Test case
Modification polyethylene glycol succinate prepared by above-described embodiment and comparative example is made respectively melting compressing tablet, and the press sheet compression of making is carried out to Mechanics Performance Testing and biodegradability test.Particularly, the tensile mechanical properties that detects these press sheet compressions according to GB/T 1040.2-2006 method is as tensile strength and elongation at break; Detect the biodegradability of these press sheet compressions according to the method for GB/T 20197-2006, and the mass loss of press sheet compression before with respect to test accounts for the weight percent of press sheet compression before test and recently represents biological degradation rate with the press sheet compression after test.
Detected result is as shown in table 1 below.
Table 1
The data of recording according to above-mentioned table 1, by embodiment 1 is compared and can be found out with comparative example 1, in the toughening modifying method of described polyethylene glycol succinate provided by the invention, owing to having added hyperbranched polymer, make the modification polyethylene glycol succinate of final preparation there is obviously higher tensile strength and elongation at break, show the toughness of obvious improvement; And modification polyethylene glycol succinate prepared by method according to the present invention has good biodegradability.
Claims (24)
1. the toughening modifying method of a polyethylene glycol succinate, the method comprises: by aliphatic polyester and hyperbranched polymer contact reacts, described aliphatic polyester contains polyethylene glycol succinate, described hyperbranched polymer is the polycondensation product of 2,2-dimethylol propionic acid and the polyvalent alcohol with at least three alcoholic extract hydroxyl groups.
2. method according to claim 1, wherein, described aliphatic polyester and the catalytic process of described hyperbranched polymer are comprised: described aliphatic polyester is heated to melting, then by the aliphatic polyester of melting and described hyperbranched polymer contact reacts.
3. method according to claim 1 and 2, wherein, described contact reacts is to carry out under the condition below 200Pa under inert atmosphere or in vacuum tightness; Described catalytic temperature is 120-240 ℃, is preferably 150-185 ℃; The described catalytic time is 0.1-10 hour, is preferably 0.5-4 hour.
4. method according to claim 1 and 2, wherein, with respect to the consumption of the polyethylene glycol succinate of 100 weight parts, the consumption of described hyperbranched polymer is 0.1-10 weight part, is preferably 0.5-3 weight part.
5. method according to claim 1 and 2, wherein, in described aliphatic polyester, take the integral molar quantity of described aliphatic polyester as benchmark, the content of polyethylene glycol succinate is 50-100 % by mole, is preferably 75-100 % by mole.
6. method according to claim 1 and 2, wherein, described aliphatic polyester also contains the aliphatic polyester except polyethylene glycol succinate; And in described aliphatic polyester, take the integral molar quantity of described aliphatic polyester as benchmark, the content of described aliphatic polyester except polyethylene glycol succinate is 0.01-50 % by mole, is preferably 10-25 % by mole; The content of polyethylene glycol succinate is 50-99.99 % by mole, is preferably 75-90 % by mole.
7. method according to claim 6, wherein, the number-average molecular weight of described aliphatic polyester except polyethylene glycol succinate is 1000-120,000, molecular weight distributing index is 1-5.
8. method according to claim 1, wherein, the number-average molecular weight of polyethylene glycol succinate is 1000-80,000, molecular weight distributing index is 1-5.
9. method according to claim 1, wherein, the number-average molecular weight of described hyperbranched polymer is 500-3000.
10. according to the method described in claim 1 or 9, wherein, described in there are at least three alcoholic extract hydroxyl groups polyvalent alcohol be at least one in TriMethylolPropane(TMP), tetramethylolmethane and glycerol.
11. methods according to claim 1 and 2, wherein, described catalytic process is carried out under the existence of chainextender, and with respect to the consumption of the polyethylene glycol succinate of 100 weight parts, the consumption of described chainextender is 0.01-6 weight part, is preferably 0.1-2 weight part.
12. methods according to claim 11, wherein, described chainextender is at least one in vulcabond, binary acid amides, binary acyl chlorides, polyvalent alcohol, polycarboxylic acid and the organic compound with at least one alcoholic extract hydroxyl group and at least one carboxyl.
The toughening modifying method of 13. 1 kinds of polyethylene glycol succinates, the method comprises: succinic acid and ethylene glycol are carried out to polycondensation, then will obtain polycondensation product and hyperbranched polymer contact reacts, described hyperbranched polymer is the polycondensation product of 2,2-dimethylol propionic acid and the polyvalent alcohol with at least three alcoholic extract hydroxyl groups.
14. methods according to claim 13, wherein, described method is also included in carries out adding in the process of polycondensation aliphatic dibasic acid except succinic acid and/or the aliphatic dihydroxy alcohol except ethylene glycol by succinic acid and ethylene glycol.
15. according to the method described in claim 13 or 14, and wherein, the mol ratio of the consumption of succinic acid and ethylene glycol is 1:1-1.5.
16. methods according to claim 14, wherein, comprising succinic acid is 1:1-1.5 with comprising ethylene glycol in the mol ratio of total consumption of interior aliphatic dihydroxy alcohol at total consumption of interior aliphatic dibasic acid.
17. according to the method described in claim 13 or 14, and wherein, the condition of described polycondensation comprises: temperature of reaction is 120-240 ℃, and the reaction times is 0.1-10 hour; Described contact reacts is to carry out under the condition below 200Pa under inert atmosphere or in vacuum tightness, and temperature of reaction is 200-240 ℃, and the reaction times is 0.1-10 hour.
18. according to the method described in claim 13 or 14, and wherein, with respect to the consumption of the succinic acid of 100 weight parts, the consumption of described hyperbranched polymer is 0.1-10 weight part, is preferably 0.5-3 weight part.
19. methods according to claim 13, wherein, the number-average molecular weight of described hyperbranched polymer is 500-3000.
20. according to the method described in claim 13 or 19, wherein, described in there are at least three alcoholic extract hydroxyl groups polyvalent alcohol be at least one in TriMethylolPropane(TMP), tetramethylolmethane and glycerol.
21. according to the method described in claim 13 or 14, and wherein, described catalytic process is carried out under the existence of chainextender, and with respect to the consumption of the succinic acid of 100 weight parts, the consumption of described chainextender is 0.01-6 weight part, is preferably 0.1-2 weight part.
22. methods according to claim 21, wherein, described chainextender is at least one in vulcabond, binary acid amides, binary acyl chlorides, polyvalent alcohol, polycarboxylic acid and the organic compound with at least one alcoholic extract hydroxyl group and at least one carboxyl.
The 23. modification polyethylene glycol succinates of being prepared by the method described in any one in claim 1-22.
24. modification polyethylene glycol succinates according to claim 23, wherein, the elongation at break of described modification polyethylene glycol succinate is 150-1500%.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105330828A (en) * | 2015-12-16 | 2016-02-17 | 中国科学院长春应用化学研究所 | Polyester elastomer, preparation method thereof and flexibilizer |
| CN105778030A (en) * | 2016-03-15 | 2016-07-20 | 济南大学 | Application of a poly(amine-ester) to modification of polyurethane leather yellowing resistance |
| CN106397757A (en) * | 2016-09-19 | 2017-02-15 | 江南大学 | Preparation of hyperbranched polyester plasticizer and application of hyperbranched polyester plasticizer in PVC (polyvinyl chloride) sealants |
| CN111499849A (en) * | 2020-05-29 | 2020-08-07 | 陕西科技大学 | Polyhydroxy hydrophilic biodegradable material and preparation method and application thereof |
| CN113999373A (en) * | 2021-12-03 | 2022-02-01 | 辽宁东盛塑业有限公司 | Polylactic acid-polyethylene glycol succinate copolymer and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1719789A1 (en) * | 2005-05-03 | 2006-11-08 | Delphi Technologies, Inc. | Hyperbranched polymer and cycloaliphatic epoxy resin thermosets |
| CN101628972A (en) * | 2008-07-14 | 2010-01-20 | 青岛生物能源与过程研究所 | Method for preparing poly (ethylene succinate) |
| US20100273295A1 (en) * | 2005-04-28 | 2010-10-28 | James Lupton Hedrick | Surface-Decorated Polymeric Amphiphile Porogens for the Templation of Nanoporous Materials |
| CN102477216A (en) * | 2010-11-26 | 2012-05-30 | 上海华明高技术（集团）有限公司 | Polybutylene succinate fully biodegradable material and preparation process thereof |
-
2012
- 2012-10-29 CN CN201210421284.2A patent/CN103788379B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100273295A1 (en) * | 2005-04-28 | 2010-10-28 | James Lupton Hedrick | Surface-Decorated Polymeric Amphiphile Porogens for the Templation of Nanoporous Materials |
| EP1719789A1 (en) * | 2005-05-03 | 2006-11-08 | Delphi Technologies, Inc. | Hyperbranched polymer and cycloaliphatic epoxy resin thermosets |
| CN101628972A (en) * | 2008-07-14 | 2010-01-20 | 青岛生物能源与过程研究所 | Method for preparing poly (ethylene succinate) |
| CN102477216A (en) * | 2010-11-26 | 2012-05-30 | 上海华明高技术（集团）有限公司 | Polybutylene succinate fully biodegradable material and preparation process thereof |
Non-Patent Citations (2)
| Title |
|---|
| 张世平等: "聚丁二酸丁二醇酯的研究进展", 《高分子通报》 * |
| 肖文清等: "超支化聚酯的研究现状", 《材料导报》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105330828A (en) * | 2015-12-16 | 2016-02-17 | 中国科学院长春应用化学研究所 | Polyester elastomer, preparation method thereof and flexibilizer |
| CN105778030A (en) * | 2016-03-15 | 2016-07-20 | 济南大学 | Application of a poly(amine-ester) to modification of polyurethane leather yellowing resistance |
| CN105778030B (en) * | 2016-03-15 | 2018-08-07 | 济南大学 | A kind of application of hyperbranched polyamine -ester in improving polyurethane leather yellowing resistance |
| CN106397757A (en) * | 2016-09-19 | 2017-02-15 | 江南大学 | Preparation of hyperbranched polyester plasticizer and application of hyperbranched polyester plasticizer in PVC (polyvinyl chloride) sealants |
| CN106397757B (en) * | 2016-09-19 | 2018-06-05 | 江南大学 | A kind of preparation of hyperbranched poly ester plasticiser and its application in PVC fluid sealants |
| CN111499849A (en) * | 2020-05-29 | 2020-08-07 | 陕西科技大学 | Polyhydroxy hydrophilic biodegradable material and preparation method and application thereof |
| CN113999373A (en) * | 2021-12-03 | 2022-02-01 | 辽宁东盛塑业有限公司 | Polylactic acid-polyethylene glycol succinate copolymer and preparation method thereof |
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|---|---|
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