CN101338025A - Polylactic acid/polyethylene terephthalate multi-block copolymer, method for preparing same and uses - Google Patents
Polylactic acid/polyethylene terephthalate multi-block copolymer, method for preparing same and uses Download PDFInfo
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Abstract
The invention discloses pla/polyethylene terephthalate segmented copolymer, which is characterized in that the copolymer is prepared by the melting reaction of low melting point polyethylene terephthalate with the melting point of 110 to 210 DEG C and the intrinsic viscosity of 0.3 to 1.5dl/g and hydroxyl at two ends and pla-prepolymer with hydroxyl at two ends and the intrinsic viscosity of 0.05 to 0.5dL/g under the presence of the coupling agent of diisocyanate. The intrinsic viscosity of the copolymer is 0.3 to 2.5 dL/g, the melting point is 110 to 210 DEG C. The invention also discloses a preparation method for the copolymer. The segmented copolymer which is provided by the invention not only has high molecular weight and good thermal stability as well as machinability, but also has excellent biodegradability of PLA and establishes the basis for the materials as the general type polymer materials. The segmented copolymer has simple method and process, low cost by adopting the direct melting method to prepare lactic acid and easy controlled reaction, and thereby can realize the scale and continuous industrial production.
Description
Technical field
The invention belongs to polyethylene terephthalate and poly(lactic acid) modification by copolymerization technical field, be specifically related to poly(lactic acid)/low melting point polyethylene terephthalate segmented copolymer and preparation method thereof and purposes.
Background technology
Polyethylene terephthalate (PET) has advantages such as good thermotolerance, chemical proofing, obdurability, electrical insulating property, security, fiber, film, engineering plastics, polyester bottles etc. have been widely used in, but because it belongs to a kind of traditional petroleum base material, not only use discarded back difficult degradation, can cause serious environmental to pollute, and because of oil price sharp rises, its cost is also constantly raising up.To this, people have carried out a large amount of study on the modification, to improve its degradation property and to reduce its cost.
Poly(lactic acid) (PLA) be a kind of be the polymkeric substance of the fully biodegradable of feedstock production with the lactic acid of renewable resources (as starch) by fermentative preparation, be described as one of biodegradable material of tool development prospect.Had bibliographical information in recent years and prepared the PET-PLA intermingling material by solution or melt-blending process, as Chinese patent CN101168617A a kind of employing diprotic acid is disclosed or dibasic alcohol carries out modification as the 3rd monomer to PET, and with the toughner of the PET after the modification as poly(lactic acid), the method that adopts blend to extrude prepares the mixture of the two.The adding of modified PET, though the elongation at break of poly(lactic acid) is increased, maximum can reach 50%.But owing to lack consistency between modified PET and the poly(lactic acid), the mechanical property of blend still is not very desirable.In addition, blending method can not fundamentally solve the problem that PET is difficult to degrade.
(Ewa Olewnik such as Olewnik, Wojciech Czerwinski, Jacek Nowaczyk, European PolymerJournal, 2007,43 (3), be raw material then 1009-1019) with lact-acid oligomer (OLLA) and ethylene glycol terephthalate (BHET), adopt direct copolymerization method to prepare the PET-PLLA multipolymer of a series of molecular weight less (all being lower than 5000).Because the boiling point of lact-acid oligomer is lower, in order to prevent its loss, they so just cause 180 ℃ of temperature as polycondensation the activity of BHET very low, thereby are difficult to generate the high-molecular weight polycondensation product with the lact-acid oligomer effecting reaction.As everyone knows, the height of molecular weight will directly affect the use properties of macromolecular material, and in general, the molecular weight of macromolecular material just has mechanical property preferably after must reaching certain numerical value.And gained PET-PLLA copolymerization product sequential structure complexity, major part is a random copolymers, does not have fusing point, its hot workability is inevitable very poor, does not have actual application value.
In addition, because the fusing point generally very high (270-280 ℃) of PET, and the thermostability of PLA is relatively poor, its maximum decomposition temperature is about 280 ℃, this just makes that PLA decomposes under the melting temperature of PET very violent, thereby carry out the conventional frit reaction with it except that being difficult under the melting temperature of PET, it is also very difficult to seek out the high-molecular weight copolymeric material.
Low-melting point PET is a kind of modified poly ester, and its fusing point is generally 100～210 ℃.Low-melting point polyester has kept the part characteristic of polyester, and itself and common PET have good consistency.In addition, it is low that low-melting point PET also has a fusing point, and characteristics such as good fluidity can be widely used in weaving, non-woven fabrics industry; Also can directly apply to industries such as building materials, coating.Preparation of low-melting point PET adopts diprotic acid or 1 such as m-phthalic acid, hexanodioic acid mostly at present, and dibasic alcohol such as 4-butyleneglycol, 1,4 cyclohexane dimethanol are as properties-correcting agent, and its preparation method also focuses mostly in adopting the direct polymerization method to be prepared.Yet when adopting the direct polymerization method, because terephthalic acid is different with di-alcohols esterification activity, hyper acid not participate in the terephthaldehyde who reacts, and causes the structure of modified PET wayward, and the circulation ratio and the controllability of reaction are relatively poor.In addition, because there is carboxyl in the PET that is obtained at the end of the chain, if carry out coupling with vulcabond, will inevitably reduce the coupling efficiency of vulcabond, this also is very disadvantageous to the molecular weight that improves multipolymer.
Summary of the invention
At the deficiencies in the prior art, the purpose of this invention is to provide a kind of polyethylene terephthalate/poly(lactic acid) segmented copolymer that can have advantages such as higher molecular weight, better thermostability and biodegradable simultaneously.
Another object of the present invention provides the method for preparation above-mentioned poly(lactic acid)/polyethylene terephthalate segmented copolymer
A further object of the present invention provides the purposes of the poly(lactic acid)/polyethylene terephthalate segmented copolymer of above preparation.
For reaching the object of the invention, avoid producing the problem that prior art occurs, to obtain the PET-PLA multipolymer of higher molecular weight, when designing, conducting molecule of the present invention at first considers the prepolymer of earlier synthetic PET and PLA, adopt the method for chain extension to prepare the multipolymer of the two then, so not only can control its each segmental chain length easily, and obtain the multipolymer of higher molecular weight easily; Secondly, the present invention considers to carry out chain extension with the more low-melting PET and the poly(lactic acid) of preparation.For this reason, poly(lactic acid) provided by the invention/polyethylene terephthalate segmented copolymer, it is characterized in that this multipolymer is is that 110～210 ℃, intrinsic viscosity are that 0.3～1.5dl/g and two ends are that the low melting point polyethylene terephthalate and the two ends of hydroxyl are that hydroxyl, intrinsic viscosity are 0.05～0.5dL/g poly(lactic acid) prepolymer with fusing point, get through the frit reaction preparation in the presence of the coupling agent vulcabond, its repeating structure is as follows:
Wherein the PLA representative structure is
Polylactic acid chain segment, x is the polymerization degree of poly(lactic acid), the PET representative structure is
Low melting point polyethylene terephthalate segment, wherein P is the hydrocarbyl portion structure of aliphatic dihydroxy alcohol, y, z are respectively the ethylene glycol terephthalate segment and the terephthalic acid binary aliphatic alcohol ester segmental polymerization degree, R represents the structure of hydrocarbyl portion in the chainextender vulcabond, m, n be respectively 〉=1 integer, the intrinsic viscosity of this multipolymer is 0.3～2.5dL/g, and fusing point is 110～220 ℃.
Because the present invention is this aliphatic/aromatic (PLA/PET) segmented copolymer that carries out copolymerization with the higher relatively low-melting point PET of good in thermal property, heat-drawn wire and the PLA with good biodegradability properties, thereby product can have PLA and PET advantage separately concurrently, promptly on the basis that keeps relative higher thermal performance of PET and mechanical property, introduced the good biological degradability of PLA, and the molecular weight of product is higher.
The method of the above-mentioned segmented copolymer of preparation provided by the invention; this method is to be that 110～210 ℃, intrinsic viscosity are that 0.3～1.5dl/g and two ends are that the low melting point ethylene glycol terephthalate of hydroxyl and two ends are that hydroxyl, intrinsic viscosity are that the poly(lactic acid) prepolymer of 0.05～0.5dL/g is as raw material with fusing point; mixed post-heating in 1: 9 in molar ratio～9: 1 to fusion; and under nitrogen protection; adding is counted 0.5～10% coupling agent vulcabond by the gross weight of preceding two kinds of raw materials, under 140～210 ℃, reacted 5～90 minutes then.
The shortcoming that exists for the low-melting point PET that overcomes prior art preparation, the low-melting point PET of using in the inventive method is to select to adopt earlier the method for transesterify, promptly prepare ethylene glycol terephthalate and terephthalic acid binary aliphatic alcohol ester with dimethyl terephthalate (DMT) (DMT) and ethylene glycol (EG) and a kind of aliphatic dihydroxy alcohol generation transesterification reaction respectively, the two generation polycondensation is prepared, so both can control the structure of product, but also can make the end group of PET be hydroxyl, guarantee that it can carry out high efficiency coupling chain extending reaction with PLA.Specifically prepare according to the following steps: the dimethyl terephthalate (DMT) and the aliphatic dihydroxy alcohol that will be 1: 2～1: 5 in molar ratio, mix with the catalyst acetic acid zinc of counting 0.05～0.5% with the dimethyl terephthalate (DMT) mass percent, in 170～180 ℃ of following transesterification reaction 3～5h; Products therefrom terephthalic acid hexylene glycol ester was mixed with ethylene glycol terephthalate in 1: 1 in molar ratio～1: 9 again, add then by the used dimethyl terephthalate (DMT) gross weight of reaction and count 0.02～0.15% The catalytic antimony trioxide, 260～285 ℃ of temperature, polycondensation 2～5h makes under pressure 20～250Pa.
The used two ends of above method are the poly(lactic acid) prepolymer of hydroxyl, are according to reference (Kari Hiltunen, Mika
Jukka V.Macromolecules 1996 (29): 8677～8682) disclosed method prepares.
The used aliphatic dihydroxy alcohol of above method is preferred 1,4-butyleneglycol, 1,8-ethohexadiol, 1,4 cyclohexane dimethanol, 1,6-hexylene glycol, 2,1, any in the 5-pentanediol.
In the used preferred '-diphenylmethane diisocyanate of coupling agent vulcabond of above method, xylylene diisocyanate, tolylene diisocyanate, dicyclohexyl methane diisocyanate, the hexamethylene diisocyanate any.
In order to investigate the molecular weight of poly(lactic acid)/polyethylene terephthalate segmented copolymer that the present invention obtains, the present invention will with terephthalic acid hexylene glycol ester/ethylene glycol terephthalate in molar ratio the intrinsic viscosity of 1/1 preparation be that the low-melting point PET of 0.46dl/g and poly(lactic acid) prepolymer that intrinsic viscosity is 0.13dl/g are raw material, according to this patent preparation method, with the tolylene diisocyanate is the PET-PLA segmented copolymer that chainextender obtains after the fusion linked reaction, carry out the molecular weight test with gel permeation chromatography (GPC), the results are shown in Table 1, and while and document (Ewa Olewnik, Wojciech Czerwinski, Jacek Nowaczyk, European Polymer Journal, 2007,43 (3), 1009-1019) molecular weight of the PET-PLA multipolymer of Gong Buing contrasts.The used number-average molecular weight measuring method of the document is the nuclear-magnetism end-group analysis, and the PET-PLA multipolymer of this patent preparation is very big owing to molecular weight, and endgroup content is few, therefore is difficult to use the end group assay.Though the molecule measuring method for testing of the two is not quite similar, the general trend that changes of molecular weight as can be seen still from comparison.
Table 1
| Multipolymer is formed PET/PLA (wt%) | The multipolymer Mn that the documents method obtains * | The multipolymer Mn that this patent method obtains |
| 80/20 | 2690 | 156966 |
| 70/30 | 1980 | 111474 |
| 60/40 | 3600 | 68096 |
| 50/50 | 3930 | 56567 |
*Ewa Olewnik，Wojciech Czerwinski，Jacek Nowaczyk，European Polymer Journal，2007，43(3)，1009-1019
The multipolymer of polyethylene terephthalate provided by the invention and poly(lactic acid) can be used as fiber (containing non-woven fabrics), all types of plastic goods, wrapping material and sizing agent material and uses.
The present invention has the following advantages:
1, PET-PLA segmented copolymer provided by the invention, compared with the prior art, molecular weight has obtained improving significantly (seeing Table 1), thereby can obtain thermostability and machining property preferably, for this material is laid a good foundation as the commodity polymer material.
2, the PET-PLA segmented copolymer that provides of the present invention can have PET and PLA advantage separately concurrently, has introduced the good biological degradability of PLA on the basis that keeps relative higher thermal performance of PET and mechanical property.
3, method provided by the invention can make a series of different degradation properties that have by the different ratios of raw materials of regulating PET/PLA, the PET-PLA segmented copolymer of thermal characteristics and machining property, the performance range broad, so this multipolymer has wider application prospect.
4, adopt the low-melting point PET of ester-interchange method preparation with the present invention, can make PET segment two ends be hydroxyl, thereby guaranteed the unicity of raw material, avoided adopting the carboxyl segment that PET contained of direct copolymerization method preparation, thereby guaranteed that linked reaction can efficiently carry out.
5, the inventive method technology is simple, adopts the poly(lactic acid) of direct scorification preparation with low cost, and reaction is easy to control, thereby can realize the industrial production of mass-producing, serialization.
Embodiment
Also the invention will be further described to provide embodiment below.Be necessary to be pointed out that at this following examples can not be interpreted as limiting the scope of the invention; if the person skilled in the art in this field makes some nonessential improvement and adjustment according to the invention described above content to the present invention, still belong to protection domain of the present invention.
In addition, the intrinsic viscosity that need to prove the product that following each embodiment obtains all is with the trichloromethane dissolving, records under 30 ℃ with Ubbelohde viscometer; Fusing point then is to be recorded by differential scanning calorimetric analysis method (DSC).
Embodiment 1
To be calculated in molar ratio as 1: 3 dimethyl terephthalate (DMT) and 1,8-ethohexadiol and count 0.2% catalyst acetic acid zinc with the dimethyl terephthalate (DMT) mass percent and mix is in 170 ℃ of following transesterification reaction 3.5h; The terephthalic acid ethohexadiol ester of gained was mixed with ethylene glycol terephthalate in 1: 1 in molar ratio, add The catalytic antimony trioxide then by the used dimethyl terephthalate (DMT) gross weight 0.05% of reaction, 260 ℃ of temperature, polycondensation 2.4h gets final product under the pressure 250Pa.The intrinsic viscosity of products therefrom is 0.12dl/g, and fusing point is 110 ℃.
With gained low-melting point PET and intrinsic viscosity is after the Hydroxyl Terminated Lactic Acid Prepolymer of 0.06dl/g was mixed in 1: 1 in molar ratio; heat temperature raising is to fusion; and the adding consumption is the coupling agent tolylene diisocyanate of low-melting point PET and lactic acid prepolymer gross weight 0.5% under nitrogen protection, then in 140 ℃ of reaction 5min discharging.The intrinsic viscosity of products therefrom is 0.31dl/g, and fusing point is 113 ℃.
Embodiment 2
To be calculated in molar ratio as 1: 2.5 dimethyl terephthalate (DMT) and 2,2-dimethyl-1, ammediol, mix with the catalyst acetic acid zinc of counting 0.08% with the dimethyl terephthalate (DMT) mass percent, in 175 ℃ of following transesterification reaction 3h, terephthalic acid-2 with gained, 2-dimethyl-1, the ammediol ester mixed with ethylene glycol terephthalate in 1: 1.22 in molar ratio, add The catalytic antimony trioxide then by the used dimethyl terephthalate (DMT) gross weight 0.04% of reaction, 265 ℃ of temperature, polycondensation 3h gets final product under the pressure 190Pa.The intrinsic viscosity of products therefrom is 0.21dl/g, and fusing point is 116 ℃.
With gained low-melting point PET and intrinsic viscosity is after the Hydroxyl Terminated Lactic Acid Prepolymer of 0.09dl/g was mixed in 1: 1 in molar ratio; heat temperature raising is to fusion; and the adding consumption is the coupling agent six methylene phenylene diisocyanates of low-melting point PET and lactic acid prepolymer gross weight 1.8% under nitrogen protection, then in 150 ℃ of reaction 30min discharging.The intrinsic viscosity of products therefrom is 0.46dl/g, and fusing point is 121 ℃.
Embodiment 3
To be calculated in molar ratio as 1: 5 dimethyl terephthalate (DMT) and 1, the 6-hexylene glycol, mix with the catalyst acetic acid zinc of counting 0.5% with the dimethyl terephthalate (DMT) mass percent, in 180 ℃ of following transesterification reaction 4.5h, the terephthalic acid hexylene glycol ester of gained was mixed with ethylene glycol terephthalate in 1: 1 in molar ratio, add the The catalytic antimony trioxide by the used dimethyl terephthalate (DMT) gross weight 0.1% of reaction then, 270 ℃ of temperature, polycondensation 4.5h gets final product under the pressure 70Pa.The intrinsic viscosity of products therefrom is 0.46dl/g, and fusing point is 121 ℃.
With gained low-melting point PET and intrinsic viscosity is after the Hydroxyl Terminated Lactic Acid Prepolymer of 0.13dl/g was mixed in 1: 9 in molar ratio; heat temperature raising is to fusion; and the adding consumption is the coupling agent tolylene diisocyanate of low-melting point PET and lactic acid prepolymer gross weight 9.7% under nitrogen protection, then in 128 ℃ of reaction 90min discharging.The intrinsic viscosity of products therefrom is 0.47dl/g, and fusing point is 128 ℃.
Embodiment 4
To be calculated in molar ratio as 1: 3 dimethyl terephthalate (DMT) and 1, the 6-hexylene glycol, mix with the catalyst acetic acid zinc of counting 0.2% with the dimethyl terephthalate (DMT) mass percent, in 175 ℃ of following transesterification reaction 4.5h, because of proportioning, the processing condition of preparation low-melting point PET are identical with embodiment 3, do not state so omit.
With gained low-melting point PET and intrinsic viscosity is after the Hydroxyl Terminated Lactic Acid Prepolymer of 0.09dl/g was mixed in 4: 1 in molar ratio; heat temperature raising is to fusion; and the adding consumption is the coupling agent '-diphenylmethane diisocyanate of low-melting point PET and lactic acid prepolymer gross weight 4.4% under nitrogen protection, then in 160 ℃ of reaction 60min discharging.The intrinsic viscosity of products therefrom is 0.99dl/g, and fusing point is 133 ℃.
Embodiment 5
To be calculated in molar ratio as 1: 4 dimethyl terephthalate (DMT) and 1,4 cyclohexane dimethanol and count 0.4% catalyst acetic acid zinc with the dimethyl terephthalate (DMT) mass percent and mix, in 170 ℃ of following transesterification reaction 3.5h; The terephthalic acid cyclohexanedimethanoester ester of gained was mixed with ethylene glycol terephthalate in 1: 1 in molar ratio, add The catalytic antimony trioxide then by the used dimethyl terephthalate (DMT) gross weight 0.02% of reaction, 270 ℃ of temperature, polycondensation 4h gets final product under the pressure 70Pa.The intrinsic viscosity of products therefrom is 0.35dl/g, and fusing point is 119 ℃.
With gained low-melting point PET and intrinsic viscosity is after the Hydroxyl Terminated Lactic Acid Prepolymer of 0.13dl/g was mixed in 4: 1 in molar ratio; heat temperature raising is to fusion; and the adding consumption is the coupling agent lysinediisocyanate of low-melting point PET and lactic acid prepolymer gross weight 5.8% under nitrogen protection, then in 160 ℃ of reaction 60min discharging.The intrinsic viscosity of products therefrom is 1.11dl/g, and fusing point is 138 ℃.
Embodiment 6
To be calculated in molar ratio as 1: 3 dimethyl terephthalate (DMT) and 1,4 cyclohexane dimethanol and count 0.5% catalyst acetic acid zinc with the dimethyl terephthalate (DMT) mass percent and mix, in 180 ℃ of following transesterification reaction 3h; Because of proportioning, the processing condition of preparation low-melting point PET are identical with embodiment 5, do not state so omit.
With gained low-melting point PET and intrinsic viscosity is after the Hydroxyl Terminated Lactic Acid Prepolymer of 0.13dl/g was mixed in 1: 2.33 in molar ratio; heat temperature raising is to fusion; and the adding consumption is the coupling agent hexamethylene diisocyanate of low-melting point PET and lactic acid prepolymer gross weight 8.5% under nitrogen protection, then in 160 ℃ of reaction 60min discharging.The intrinsic viscosity of products therefrom is 0.75dl/g, and fusing point is 131 ℃.
Embodiment 7
To be calculated in molar ratio as 1: 4 dimethyl terephthalate (DMT) and 2,5-hexylene glycol and count 0.12% catalyst acetic acid zinc with the dimethyl terephthalate (DMT) mass percent and mix is in 170 ℃ of following transesterification reaction 5h; Terephthalic acid-2 with gained, 5-hexylene glycol ester mixed with ethylene glycol terephthalate in 1: 1.86 in molar ratio, add the The catalytic antimony trioxide by the used dimethyl terephthalate (DMT) gross weight 0.15% of reaction then, 270 ℃ of temperature, polycondensation 4h gets final product under the pressure 70Pa.The intrinsic viscosity of products therefrom is 0.37dl/g, and fusing point is 133 ℃.
With gained low-melting point PET and intrinsic viscosity is after the Hydroxyl Terminated Lactic Acid Prepolymer of 0.21dl/g was mixed in 1: 2.33 in molar ratio; heat temperature raising is to fusion; and the adding consumption is the coupling agent tolylene diisocyanate of low-melting point PET and lactic acid prepolymer gross weight 5.8% under nitrogen protection, then in 160 ℃ of reaction 70min discharging.The intrinsic viscosity of products therefrom is 1.22dl/g, and fusing point is 146 ℃.
Embodiment 8
To be calculated in molar ratio as 1: 3.5 dimethyl terephthalate (DMT) and 1,4 cyclohexane dimethanol and count 0.3% catalyst acetic acid zinc with the dimethyl terephthalate (DMT) mass percent and mix, in 175 ℃ of following transesterification reaction 5h; The terephthalic acid cyclohexanedimethanoester ester of gained was mixed with ethylene glycol terephthalate in 1: 2.33 in molar ratio, add The catalytic antimony trioxide then by the used dimethyl terephthalate (DMT) gross weight 0.02% of reaction, 270 ℃ of temperature, polycondensation 4.5h gets final product under the pressure 70Pa.The intrinsic viscosity of products therefrom is 0.48dl/g, and fusing point is 164 ℃.
With gained low-melting point PET and intrinsic viscosity is after the Hydroxyl Terminated Lactic Acid Prepolymer of 0.21dl/g was mixed in 1.5: 1 in molar ratio; heat temperature raising is to fusion; and the adding consumption is the coupling agent dicyclohexyl methane diisocyanate of low-melting point PET and lactic acid prepolymer gross weight 6.5% under nitrogen protection, then in 175 ℃ of reaction 70min discharging.The intrinsic viscosity of products therefrom is 1.31dl/g, and fusing point is 169 ℃.
Embodiment 9
To be calculated in molar ratio as 1: 2 dimethyl terephthalate (DMT) and 1,8-ethohexadiol and count 0.06% catalyst acetic acid zinc with the dimethyl terephthalate (DMT) mass percent and mix is in 175 ℃ of following transesterification reaction 4.5h; The terephthalic acid ethohexadiol ester of gained was mixed with ethylene glycol terephthalate in 1: 2.33 in molar ratio, add then by The catalytic antimony trioxide by the used dimethyl terephthalate (DMT) gross weight 0.03% of reaction, 280 ℃ of temperature, polycondensation 5h gets final product under the pressure 60Pa.The intrinsic viscosity of products therefrom is 0.55dl/g, and fusing point is 172 ℃.
With gained low-melting point PET and intrinsic viscosity is after the Hydroxyl Terminated Lactic Acid Prepolymer of 0.32dl/g was mixed in 2.33: 1 in molar ratio; heat temperature raising is to fusion; and the adding consumption is the coupling agent '-diphenylmethane diisocyanate of low-melting point PET and lactic acid prepolymer gross weight 6.5% under nitrogen protection, then in 185 ℃ of reaction 70min discharging.The intrinsic viscosity of products therefrom is 1.44dl/g, and fusing point is 178 ℃.
Embodiment 10
To be calculated in molar ratio as 1: 2.2 dimethyl terephthalate (DMT) and 1,8-ethohexadiol and count 0.2% catalyst acetic acid zinc with the dimethyl terephthalate (DMT) mass percent and mix is in 170 ℃ of following transesterification reaction 3.5h; Because of proportioning, the processing condition of preparation low-melting point PET are identical with embodiment 9, do not state so omit.
With gained low-melting point PET and intrinsic viscosity is after the Hydroxyl Terminated Lactic Acid Prepolymer of 0.44dl/g was mixed in 1: 1.5 in molar ratio; heat temperature raising is to fusion; and the adding consumption is the coupling agent dicyclohexyl methane diisocyanate of low-melting point PET and lactic acid prepolymer gross weight 7.7% under nitrogen protection, then in 185 ℃ of reaction 70min discharging.The intrinsic viscosity of products therefrom is 1.26dl/g, and fusing point is 155 ℃.
Embodiment 11
To be calculated in molar ratio as 1: 5 dimethyl terephthalate (DMT) and 1,5-pentanediol and count 0.45% catalyst acetic acid zinc with the dimethyl terephthalate (DMT) mass percent and mix is in 170 ℃ of following transesterification reaction 5h; The terephthalic acid pentadiol ester of gained was mixed with ethylene glycol terephthalate in 1: 3 in molar ratio, add The catalytic antimony trioxide then by the used dimethyl terephthalate (DMT) gross weight 0.11% of reaction, 280 ℃ of temperature, polycondensation 5h gets final product under the pressure 50Pa.The intrinsic viscosity of products therefrom is 0.63dl/g, and fusing point is 180 ℃.
With gained low-melting point PET and intrinsic viscosity is after the Hydroxyl Terminated Lactic Acid Prepolymer of 0.44dl/g was mixed in 2.33: 1 in molar ratio; heat temperature raising is to fusion; and the adding consumption is the coupling agent isophorone diisocyanate of low-melting point PET and lactic acid prepolymer gross weight 7.7% under nitrogen protection, then in 190 ℃ of reaction 80min discharging.The intrinsic viscosity of products therefrom is 1.61dl/g, and fusing point is 189 ℃.
Embodiment 12
To be calculated in molar ratio as 1: 3 dimethyl terephthalate (DMT) and 1,5-pentanediol and count 0.3% catalyst acetic acid zinc with the dimethyl terephthalate (DMT) mass percent and mix is in 170 ℃ of following transesterification reaction 3.5h; Because of proportioning, the processing condition of preparation low-melting point PET are identical with embodiment 11, do not state so omit.
With gained low-melting point PET and intrinsic viscosity is after the Hydroxyl Terminated Lactic Acid Prepolymer of 0.44dl/g was mixed in 9: 1 in molar ratio; heat temperature raising is to fusion; and the adding consumption is the coupling agent hexamethylene diisocyanate of low-melting point PET and lactic acid prepolymer gross weight 6.5% under nitrogen protection, then in 190 ℃ of reaction 80min discharging.The intrinsic viscosity of products therefrom is 1.83dl/g, and fusing point is 192 ℃.
Embodiment 13
To be calculated in molar ratio as 1: 2.5 dimethyl terephthalate (DMT) and 1,4-butyleneglycol and count 0.45% catalyst acetic acid zinc with the dimethyl terephthalate (DMT) mass percent and mix is in 175 ℃ of following transesterification reaction 5h; The mutual-phenenyl two acid bromide two alcohol ester of gained was mixed with ethylene glycol terephthalate in 1: 4 in molar ratio, add The catalytic antimony trioxide then by the used dimethyl terephthalate (DMT) gross weight 0.05% of reaction, 280 ℃ of temperature, polycondensation 5h gets final product under the pressure 30Pa.The intrinsic viscosity of products therefrom is 0.76dl/g, and fusing point is 194 ℃.
With gained low-melting point PET and intrinsic viscosity is after the Hydroxyl Terminated Lactic Acid Prepolymer of 0.50dl/g was mixed in 1: 1 in molar ratio; heat temperature raising is to fusion; and the adding consumption is the coupling agent xylylene diisocyanate of low-melting point PET and lactic acid prepolymer gross weight 6.5% under nitrogen protection, then in 200 ℃ of reaction 60min discharging.The intrinsic viscosity of products therefrom is 1.76dl/g, and fusing point is 205 ℃.
Embodiment 14
To be calculated in molar ratio as 1: 3 dimethyl terephthalate (DMT) and 1,4-butyleneglycol and count 0.25% catalyst acetic acid zinc with the dimethyl terephthalate (DMT) mass percent and mix is in 175 ℃ of following transesterification reaction 3.5h; Because of proportioning, the processing condition of preparation low-melting point PET are identical with embodiment 14, do not state so omit.
With gained low-melting point PET and intrinsic viscosity is after the Hydroxyl Terminated Lactic Acid Prepolymer of 0.50dl/g was mixed in 2: 1 in molar ratio; heat temperature raising is to fusion; and the adding consumption is the coupling agent dicyclohexyl methane diisocyanate of low-melting point PET and lactic acid prepolymer gross weight 6.5% under nitrogen protection, then in 200 ℃ of reaction 60min discharging.The intrinsic viscosity of products therefrom is 2.15dl/g, and fusing point is 211 ℃.
Embodiment 15
To be calculated in molar ratio as 1: 3 dimethyl terephthalate (DMT) and 2 and count 0.3% catalyst acetic acid zinc with the dimethyl terephthalate (DMT) mass percent and mix, in 175 ℃ of following transesterification reaction 3.5h; Terephthalic acid-2 with gained, 2-dimethyl-1, the ammediol ester mixed with ethylene glycol terephthalate in 1: 5.67 in molar ratio, add The catalytic antimony trioxide then by the used dimethyl terephthalate (DMT) gross weight 0.03% of reaction, 285 ℃ of temperature, polycondensation 5h gets final product under the pressure 30Pa.The intrinsic viscosity of products therefrom is 0.88dl/g, and fusing point is 209 ℃.
With gained low-melting point PET and intrinsic viscosity is after the Hydroxyl Terminated Lactic Acid Prepolymer of 0.50dl/g was mixed in 4: 1 in molar ratio; heat temperature raising is to fusion; and the adding consumption is the coupling agent isophorone diisocyanate of low-melting point PET and lactic acid prepolymer gross weight 5.8% under nitrogen protection, then in 210 ℃ of reaction 60min discharging.The intrinsic viscosity of products therefrom is 2.47dl/g, and fusing point is 218 ℃.
Embodiment 16
To be calculated in molar ratio as 1: 2 dimethyl terephthalate (DMT) and 2 and count 0.4% catalyst acetic acid zinc with the dimethyl terephthalate (DMT) mass percent and mix, in 175 ℃ of following transesterification reaction 3h; Because of proportioning, the processing condition of preparation low-melting point PET are identical with embodiment 15, do not state so omit.
With gained low-melting point PET and intrinsic viscosity is after the Hydroxyl Terminated Lactic Acid Prepolymer of 0.50dl/g was mixed in 1.5: 1 in molar ratio; heat temperature raising is to fusion; and the adding consumption is the coupling agent xylylene diisocyanate of low-melting point PET and lactic acid prepolymer gross weight 5.8% under nitrogen protection, then in 210 ℃ of reaction 60min discharging.The intrinsic viscosity of products therefrom is 2.21dl/g, and fusing point is 213 ℃.
Claims (6)
1, a kind of poly(lactic acid)/polyethylene terephthalate segmented copolymer, it is characterized in that this multipolymer is is that 110～210 ℃, intrinsic viscosity are that 0.3～1.5dl/g and two ends are that the low melting point polyethylene terephthalate and the two ends of hydroxyl are that hydroxyl, intrinsic viscosity are 0.05～0.5dL/g poly(lactic acid) prepolymer with fusing point, get through the frit reaction preparation in the presence of the coupling agent vulcabond, its repeating structure is as follows:
Wherein the PLA representative structure is
Polylactic acid chain segment, x is the polymerization degree of poly(lactic acid), the PET representative structure is
Low melting point polyethylene terephthalate segment, wherein P is the hydrocarbyl portion structure of aliphatic dihydroxy alcohol, y, z are respectively the ethylene glycol terephthalate segment and the terephthalic acid binary aliphatic alcohol ester segmental polymerization degree, R represents the structure of hydrocarbyl portion in the chainextender vulcabond, m, n be respectively 〉=1 integer, the intrinsic viscosity of this multipolymer is 0.3～2.5dL/g, and fusing point is 110～220 ℃.
2, a kind of method for preparing the described segmented copolymer of claim 1; this method is to be that 110～210 ℃, intrinsic viscosity are that 0.3～1.5dl/g and two ends are that the low melting point ethylene glycol terephthalate of hydroxyl and two ends are that hydroxyl, intrinsic viscosity are that the poly(lactic acid) prepolymer of 0.05～0.5dL/g is as raw material with fusing point; mixed post-heating in 1: 9 in molar ratio～9: 1 to fusion; and under nitrogen protection; adding is counted 0.5～10% coupling agent vulcabond by the gross weight of preceding two kinds of raw materials, reacts down at 140～210 ℃ then to make in 5～90 minutes.
3, the method for preparing segmented copolymer according to claim 2, the used two ends of this method are that the low melting point polyethylene terephthalate of hydroxyl is dimethyl terephthalate (DMT) and the aliphatic dihydroxy alcohol that will be calculated in molar ratio as 1: 2～1: 5, mix with the catalyst acetic acid zinc of counting 0.05～0.5% with the dimethyl terephthalate (DMT) mass percent, in 170～180 ℃ of following transesterification reaction 3～5h; Products therefrom terephthalic acid binary aliphatic alcohol ester was mixed with ethylene glycol terephthalate in 1: 1 in molar ratio～1: 9 again, add then by the used dimethyl terephthalate (DMT) gross weight of reaction and count 0.02～0.15% The catalytic antimony trioxide, 260～285 ℃ of temperature, polycondensation 2～5h gets final product under pressure 20～250Pa.
4, the method for preparing segmented copolymer according to claim 3, used aliphatic dihydroxy alcohol is 1 in this method, 4-butyleneglycol, 1,8-ethohexadiol, 1,4-cyclohexanedimethanol, 1,6-hexylene glycol, 2,2-dimethyl-1, ammediol, 1, any in the 5-pentanediol.
5, according to claim 1 or 2 or the 3 or 4 described methods that prepare segmented copolymer, the used coupling agent vulcabond of this method is any in '-diphenylmethane diisocyanate, xylylene diisocyanate, tolylene diisocyanate, dicyclohexyl methane diisocyanate, the hexamethylene diisocyanate.
6, the multipolymer of the polyethylene terephthalate of claim 1 qualification and poly(lactic acid) is as the application of fiber, non-woven fabrics, all types of plastic goods, wrapping material and sizing agent material.
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