CN101768246A - Multi-block copolyesters and preparation method thereof - Google Patents
Multi-block copolyesters and preparation method thereof Download PDFInfo
- Publication number
- CN101768246A CN101768246A CN201010028100A CN201010028100A CN101768246A CN 101768246 A CN101768246 A CN 101768246A CN 201010028100 A CN201010028100 A CN 201010028100A CN 201010028100 A CN201010028100 A CN 201010028100A CN 101768246 A CN101768246 A CN 101768246A
- Authority
- CN
- China
- Prior art keywords
- prepolymer
- block copolyesters
- hydroxy group
- vulcabond
- terminal hydroxy
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses multi-block copolyesters. In a structure formula of the multi-block copolyesters, R is an alkyl part of diisocyanate, all the x, a and b are the integers from 2 to 10, y and c are the integers from 0 to 8, wherein when x is equal to b, y is not equal to c; when y is equal to c, x is not equal to b; and all the j, k and n are the integers more than 5. A limiting viscosity number of the multi-block copolyesters is 0.7 to 4.7 dL/g, the melting point is 70 to 240 DEG C, the tensile strength is 10 to 67 Mpa and the elongation at break is 20% to 1100%. The invention also discloses a method for preparing the multi-block copolyesters. The multi-block copolyesters prepared by using the method of the invention are characterized by high melting point and molecular weight, excellent mechanical property, better controllability and repeatability than the controllability and repeatability of the copolyesters prepared by the traditional ester exchange method and wider application range.
Description
Technical field
The invention belongs to blocked copolyester and preparation method thereof technical field.
Background technology
Because being extensive use of of conventional plastic material, plastic pollution problem are severe day by day.Aliphatic polyester has been subjected to people's favor as a class environmental friendliness Biodegradable material.But because high-molecular aliphatic polyester is difficult to adopt ordinary method preparation, and its mechanical property and thermostability are relatively poor, have seriously restricted the application of aliphatic polyester.Therefore, in order to expand the range of application of aliphatic polyester, need to improve the molecular weight of aliphatic polyester, and aliphatic polyester is carried out modification.
With other monomer or polymkeric substance copolymerization be to improve one of common method of aliphatic polyester performance.As (Amin Cao such as Amin Cao, Takashi Okamura, Kazuo Nakayama, Yoshio Inoue, Takashi Masuda.PolymDegrad Stab 2002 (78): 107～117) adopt the direct polymerization method to synthesize the polyethylene glycol succinate/poly butylene succinate multipolymer of higher molecular weight.Yet this multipolymer is a random copolymers, its crystal property has been subjected to seriously influencing, make the multipolymer fusing point reduce much than its corresponding homopolymer, especially in the time of about the EGS ethylene glycol succinate components contents reaches 50%, the fusing point of multipolymer is reduced to 56 ℃, and this can influence the range of application of copolymeric material undoubtedly.And for example patent CN 1434067A discloses employing organic silazane hydride compounds and has come the synthesizing polyester multipolymer as chainextender, its specific practice is earlier dibasic alcohol and diprotic acid to be carried out polycondensation to prepare the hydroxyl terminated prepolymer that molecular weight is 1000～2000g/mol, carry out chain extending reaction with the organic silazane hydride compounds as chainextender then, prepared copolyesters, yet because the organosilazanes activity is lower, chain extension efficient is relatively poor, and the copolyesters molecular weight of preparation is lower.In addition, the chain extending reaction time that this method requires is long, and reaction has the ammonia generation, can cause topsoil.
For aliphatic polyester, aromatic polyester has better thermal characteristics and mechanical property, but the degradation property of aromatic polyester is poor.In order to improve the biological degradability of aromatic polyester, people have introduced the aliphatics composition in aromatic polyester, Ecoflex series aliphatic-aromatic copolyester as BASF AG's research and development, be exactly after introducing the aliphatic polyester segment, make the biological degradability of aromatic copolyester obtain very big improvement, and the mechanical property excellence of multipolymer.But this multipolymer is because of also being random copolymers, and fusing point is also lower, is approximately 120 ℃, and is a lot of with respect to having reduced the fusing point (greater than 200 ℃) of the aromatic polyester of homopolymerization.
As everyone knows, for random copolymers, the crystal property of segmented copolymer, fusing point and mechanical property are all better.The synthetic method of olefines segmented copolymer is often comparatively ripe again, but polyester type block copolymer and preparation method thereof then and imperfection, the method that bibliographical information is maximum is an ester-interchange method, promptly adopts two kinds of high-molecular weight polyester under catalyzer and high temperature transesterification reaction to take place.Though this method can prepare blocked copolyester, but still have following defectives, at first, the degree of transesterification reaction is difficult to control, and especially when the transesterify degree is too big even what obtain is atactic polyester, so this method circulation ratio is relatively poor; Secondly, react under comparatively high temps, the thermal destruction of polyester is obvious, therefore can reduce the molecular weight of polyester, and then reduce its mechanical property.
Summary of the invention
At the deficiencies in the prior art, primary and foremost purpose of the present invention is the multi-block copolyesters that design provides a kind of high-melting-point, high limiting viscosity number and mechanical property excellence.
But another object of the present invention provides the method for the above-mentioned multi-block copolyesters of preparation.
The multi-block copolyesters that the present invention's design provides, its general structure is:
Or
In the formula, R represents the hydrocarbyl portion of vulcabond, and x, a, b are 2～10 integer, y, c are 0～8 integer, and during x=b, y ≠ c is during y=c, x ≠ b, j, k, n are the integer greater than 5, and the limiting viscosity number of this multi-block copolyesters is 0.7～4.7dL/g, and fusing point is 70～240 ℃, tensile strength is 10～67MPa, and elongation at break is 20～1100%.
The method of the multi-block copolyesters that preparation provided by the invention is above-mentioned; this method is earlier with prepolymer I and prepolymer II intensification fusion and stirring under protection of inert gas; add vulcabond then; got final product in 5 minutes～10 hours 90～270 ℃ of frit reactions; preferably 150～270 ℃ of frit reactions 5 minutes～5 hours; wherein prepolymer I and prepolymer II count 1～10: 1～10 by weight; the vulcabond consumption counts 0.5～10% by prepolymer I and prepolymer II gross weight; or with prepolymer I; after prepolymer II and vulcabond premix are even; under protection of inert gas, react extruding pelletization or directly make product through forcing machine in 70～270 ℃; the residence time of raw material in forcing machine is 1～30 minute; wherein prepolymer I and prepolymer II count 1～10: 1～10 by weight, and the vulcabond consumption counts 0.5～10% by prepolymer I and prepolymer II gross weight.
Used prepolymer I is the terminal hydroxy group aliphatic polyester in the aforesaid method, and its structural formula is:
B is 2～10 integer in the formula, and c is 0～8 integer, and n is the integer greater than 5; Used prepolymer II is terminal hydroxy group aromatic polyester or another kind of terminal hydroxy group aliphatic polyester, and its structural formula is respectively:
A and x are 2～10 integer in the formula, and y is 0～8 integer, and k and j are the integer greater than 5, and used prepolymer II is when being another kind of terminal hydroxy group aliphatic polyester, during x=b in prepolymer I and the prepolymer II structural formula, and y ≠ c, during y=c, x ≠ b.
Used prepolymer can adopt the direct polycondensation method preparation in the aforesaid method, when dibasic alcohol is excessive in the feed composition, just can prepare the hydroxyl telechelic polyester prepolymer by the polycondensation method.
Used vulcabond is 1 in the aforesaid method, any in 6-hexamethylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate or the dicyclohexyl methane diisocyanate.
The present invention has the following advantages:
1, because the copolyesters of the present invention's preparation is a multi-block copolyesters, thereby no matter be the aliphatics blocked copolyester, or aliphatic-aromatic blocked copolyester, its fusing point or (adopt the PBS/PES multipolymer of direct polycondensation method preparation than the fusing point height of the corresponding copolyesters of direct polymerization method preparation, when the EGS ethylene glycol succinate component concentration is 50%, the fusing point of multipolymer only is 56 ℃, and the present invention prepares the PBS/PES segmented copolymer fusing point of similar proportion is 105 ℃), or than the fusing point height of corresponding random copolymers (the Ecoflex series aliphatic-aromatic copolyester fusing point as BASF AG is about 120 ℃, and the aliphatic-aromatic multi-block copolyesters fusing point of the present invention preparation reaches as high as more than 200 ℃), make its range of application can be more extensive.
2, because preparation method provided by the invention is to be raw material with the low-molecular-weight polyester prepolymer, with the vulcabond is chainextender, adopt the multi-block copolyesters of chain extension method preparation, thereby not only expanded a kind of new method for preparing multi-block copolyesters, and the multi-block copolyesters molecular weight height that is obtained, avoided traditional ester-interchange method to prepare multi-block copolyesters and reduced problem because of the molecular weight that thermal destruction causes.
3, because method provided by the invention is the chain extension method, thereby the controllability of its preparation multi-block copolyesters is all better than traditional ester-interchange method with repeatability,
4, because preparation method provided by the invention is that the employing vulcabond is a chainextender, thereby chain extension excellent in efficiency not only, the multi-block copolyesters molecular weight height of preparation, and the chain extending reaction time that requires is short, do not have ammonia to generate in the reaction process, can not cause topsoil.
5, multi-block copolyesters mechanical property provided by the invention is adjustable, and therefore, this copolyesters has broad application prospects.
Embodiment
Provide embodiment below so that invention is further described.It is important to point out that following examples can not be interpreted as limiting the scope of the invention, if this technical field skilled person according to the invention described above content to improvement and adjustment that the present invention makes some non-intrinsically safes, still belong to protection domain of the present invention.
In addition, what deserves to be explained is also that embodiment 1-8, the intrinsic viscosity of the multi-block copolyesters of 14-17 gained after product is dissolved with trichloromethane, record under 25 ℃ with Ubbelodhe viscometer; Embodiment 9-13, the intrinsic viscosity of the multi-block copolyesters of 18,19 gained after product is dissolved with phenol/tetrachloroethane (volume ratio 1: 1), record under 25 ℃ with Ubbelodhe viscometer; The fusing point of gained multi-block copolyesters is to record by dsc; The mechanical property of gained multi-block copolyesters be with product its more than fusing point on 20 ℃ of vulcanizing presses hot pressing make the film that thickness is 0.5mm, record according to GB/T 1040-92 standard then.
Embodiment 1
Earlier be that the terminal hydroxy group polyethylene glycol succinate of 0.11dL/g and terminal hydroxy group poly adipate succinic acid ester that intrinsic viscosity is 0.13dL/g are to weigh at 5: 5 and place reaction unit by weight with intrinsic viscosity; after its complete fusion is treated in the stirring intensification under nitrogen protection then; adding consumption again is the chainextender tolylene diisocyanate of prepolymer total amount 10%; 150 ℃ of frit reactions 5 minutes, promptly get product.
The intrinsic viscosity of products therefrom is 1.05dL/g; Fusing point is 83.5 ℃; The tensile strength of film is 34.83MPa, and elongation at break is 537%.
Embodiment 2
Earlier be that the terminal hydroxy group poly-succinic hexylene glycol ester of 0.14dL/g and terminal hydroxy group polyethylene glycol succinate that intrinsic viscosity is 0.17dL/g are to weigh at 7: 3 and place reaction unit by weight with intrinsic viscosity; after its complete fusion is treated in the stirring intensification under nitrogen protection then; adding consumption again is the chainextender dicyclohexyl methane diisocyanate of prepolymer total amount 8.6%; 160 ℃ of frit reactions 30 minutes, promptly get product.
The intrinsic viscosity of products therefrom is 1.34dL/g; Fusing point is 84.3 ℃; The tensile strength of film is 38.65MPa, and elongation at break is 610%.
Embodiment 3
Earlier be that the terminal hydroxy group polyethylene glycol succinate of 0.16dL/g and terminal hydroxy group poly butylene succinate that intrinsic viscosity is 0.17dL/g are to weigh at 5: 5 and place reaction unit by weight with intrinsic viscosity; after its complete fusion is treated in the stirring intensification under nitrogen protection then; adding consumption again is the chainextender 1 of prepolymer total amount 4.8%; the 6-hexamethylene diisocyanate; 170 ℃ of frit reactions 1 hour, promptly get product.
The intrinsic viscosity of products therefrom is 1.35dL/g; Fusing point is 105.6 ℃; The tensile strength of film is 58.68MPa, and elongation at break is 1080%.
Embodiment 4
Earlier be that the poly-hexanodioic acid ethohexadiol ester of terminal hydroxy group of 0.19dL/g and terminal hydroxy group poly-succinic certain herbaceous plants with big flowers diol ester that intrinsic viscosity is 0.20dL/g are to weigh at 1: 10 and place reaction unit by weight with intrinsic viscosity; after its complete fusion is treated in the stirring intensification under nitrogen protection then; adding consumption again is the chainextender tolylene diisocyanate of prepolymer total amount 4.2%; 170 ℃ of frit reactions 2 hours, promptly get product.
The intrinsic viscosity of products therefrom is 2.29dL/g; Fusing point is 82.1 ℃; The tensile strength of film is 10.73MPa, and elongation at break is 733%.
Embodiment 5
Earlier be that the terminal hydroxy group polyethylene glycol suberate of 0.22dL/g and the poly-certain herbaceous plants with big flowers diacid butanediol ester of terminal hydroxy group that intrinsic viscosity is 0.24dL/g are to weigh at 7: 3 and place reaction unit by weight with intrinsic viscosity; after its complete fusion is treated in the stirring intensification under nitrogen protection then; adding consumption again is the chainextender xylylene diisocyanate of prepolymer total amount 3.6%; 160 ℃ of frit reactions 2 hours, promptly get product.
The intrinsic viscosity of products therefrom is 1.68dL/g; Fusing point is 78.9 ℃; The tensile strength of film is 29.33MPa, and elongation at break is 752%.
Embodiment 6
Earlier be that the terminal hydroxy group poly-succinic hexylene glycol ester of 0.24dL/g and the poly-hexanodioic acid hexylene glycol ester of terminal hydroxy group that intrinsic viscosity is 0.28dL/g are to weigh at 5: 5 and place reaction unit by weight with intrinsic viscosity; after its complete fusion is treated in the stirring intensification under nitrogen protection then; adding consumption again is the chainextender 1 of prepolymer total amount 2.1%; the 6-hexamethylene diisocyanate; 90 ℃ of frit reactions 10 hours, promptly get product.
The intrinsic viscosity of products therefrom is 3.64dL/g; Fusing point is 75.3 ℃; The tensile strength of film is 28.92MPa, and elongation at break is 623%.
Embodiment 7
Earlier be that the poly-hexanodioic acid ethohexadiol ester of terminal hydroxy group of 0.30dL/g and the poly-certain herbaceous plants with big flowers diacid hexylene glycol ester of terminal hydroxy group that intrinsic viscosity is 0.38dL/g are to weigh at 10: 1 and place reaction unit by weight with intrinsic viscosity; after its complete fusion is treated in the stirring intensification under nitrogen protection then; adding consumption again is the chainextender tolylene diisocyanate of prepolymer total amount 1.5%; 110 ℃ of frit reactions 7 hours, promptly get product.
The intrinsic viscosity of products therefrom is 3.87dL/g; Fusing point is 73.8 ℃; The tensile strength of film is 28.95MPa, and elongation at break is 679%.
Embodiment 8
Earlier be that the terminal hydroxy group polyethylene glycol succinate of 0.40dL/g and terminal hydroxy group poly butylene succinate that intrinsic viscosity is 0.48dL/g are to weigh at 5: 5 and place reaction unit by weight with intrinsic viscosity; after its complete fusion is treated in the stirring intensification under nitrogen protection then; adding consumption again is the chainextender dicyclohexyl methane diisocyanate of prepolymer total amount 0.5%; 130 ℃ of frit reactions 5 hours, promptly get product.
The intrinsic viscosity of products therefrom is 4.62dL/g; Fusing point is 105.3 ℃; The tensile strength of film is 55.32MPa, and elongation at break is 763%.
Embodiment 9
Earlier be that the terminal hydroxy group polyethylene glycol succinate of 0.11dL/g and terminal hydroxy group polyethylene terephthalate that intrinsic viscosity is 0.15dL/g are to weigh at 1: 9 and place reaction unit by weight with intrinsic viscosity; after its complete fusion is treated in the stirring intensification under nitrogen protection then; adding consumption again is the chainextender tolylene diisocyanate of prepolymer total amount 9.0%; 270 ℃ of frit reactions 15 minutes, promptly get product.
The intrinsic viscosity of products therefrom is 0.70dL/g; Fusing point is 240 ℃; The tensile strength of film is 45.32MPa, and elongation at break is 20%.
Embodiment 10
Earlier be that the terminal hydroxy group poly-succinic certain herbaceous plants with big flowers diol ester of 0.15dL/g and the poly-m-phthalic acid hexylene glycol ester of terminal hydroxy group that intrinsic viscosity is 0.20dL/g are to weigh at 3: 7 and place reaction unit by weight with intrinsic viscosity; after its complete fusion is treated in the stirring intensification under nitrogen protection then; adding consumption again is the chainextender dicyclohexyl methane diisocyanate of prepolymer total amount 7.4%; 210 ℃ of frit reactions 1 hour, promptly get product.
The intrinsic viscosity of products therefrom is 1.60dL/g; Fusing point is 195.6 ℃; The tensile strength of film is 52.26MPa, and elongation at break is 799%.
Embodiment 11
Earlier be that the terminal hydroxy group poly adipate succinic acid ester of 0.18dL/g and the poly-O-phthalic acid propylene glycol ester of terminal hydroxy group that intrinsic viscosity is 0.25dL/g are to weigh at 10: 1 and place reaction unit by weight with intrinsic viscosity; after its complete fusion is treated in the stirring intensification under nitrogen protection then; adding consumption again is the chainextender xylylene diisocyanate of prepolymer total amount 5.8%; 240 ℃ of frit reactions 5 hours, promptly get product.
The intrinsic viscosity of products therefrom is 1.82dL/g; Fusing point is 100.5 ℃; The tensile strength of film is 17.73MPa, and elongation at break is 374%.
Embodiment 12
Earlier be that the poly-suberic acid hexylene glycol ester of terminal hydroxy group of 0.30dL/g and terminal hydroxy group poly terephthalic acid certain herbaceous plants with big flowers diol ester that intrinsic viscosity is 0.35dL/g are to weigh at 1: 10 and place reaction unit by weight with intrinsic viscosity; after its complete fusion is treated in the stirring intensification under nitrogen protection then; adding consumption again is the chainextender tolylene diisocyanate of prepolymer total amount 3.9%; 200 ℃ of frit reactions 2 hours, promptly get product.
The intrinsic viscosity of products therefrom is 1.53dL/g; Fusing point is 188.2 ℃; The tensile strength of film is 66.48MPa, and elongation at break is 400%.
Embodiment 13
Earlier be that the terminal hydroxy group poly-succinic hexylene glycol ester of 0.47dL/g and terminal hydroxy group polybutylene terephthalate that intrinsic viscosity is 0.50dL/g are to weigh at 7: 3 and place reaction unit by weight with intrinsic viscosity; after its complete fusion is treated in the stirring intensification under nitrogen protection then; adding consumption again is the chainextender dicyclohexyl methane diisocyanate of prepolymer total amount 0.5%; 230 ℃ of frit reactions 5 hours, promptly get product.
The intrinsic viscosity of products therefrom is 1.37dL/g; Fusing point is 123.5 ℃; The tensile strength of film is 44.25MPa, and elongation at break is 168%.
Embodiment 14
With intrinsic viscosity is that the poly-hexanodioic acid ethohexadiol ester of the terminal hydroxy group polyethylene glycol succinate of 0.11dL/g and terminal hydroxy group that intrinsic viscosity is 0.14dL/g was by weight weighing in 5: 5; and with consumption be 1 of prepolymer total amount 10%; after the 6-hexamethylene diisocyanate places mixer pre-mixing evenly together; directly pass through charging machine; adding the twin screw extruder reaction under nitrogen protection extrudes; granulation or directly through blowing; injection moulding; plastic uptake; calendering technology is processed into corresponding goods; each section of twin screw extruder temperature is: 70 ℃ of feeding sections; 150 ℃ of melt zones; 100 ℃ of discharge ports, raw material is 1 minute by the time of forcing machine.
The intrinsic viscosity of products therefrom is 0.86dL/g; Fusing point is 85.4 ℃; The tensile strength of film is 37.63MPa, and elongation at break is 432%.
Embodiment 15
With intrinsic viscosity is that the terminal hydroxy group poly butylene succinate of 0.19dL/g and terminal hydroxy group polyethylene glycol succinate that intrinsic viscosity is 0.24dL/g were by weight weighing in 3: 7; and be after the tolylene diisocyanate of prepolymer total amount 7.9% places mixer pre-mixing evenly with consumption; directly pass through charging machine; adding the twin screw extruder reaction under nitrogen protection extrudes; granulation or directly through blowing; injection moulding; plastic uptake; calendering technology is processed into corresponding goods; each section of twin screw extruder temperature is: 80 ℃ of feeding sections; 160 ℃ of melt zones; 110 ℃ of discharge ports, raw material is 10 minutes by the time of forcing machine.
The intrinsic viscosity of products therefrom is 1.46dL/g; Fusing point is 101.2 ℃; The tensile strength of film is 43.82MPa, and elongation at break is 679%.
Embodiment 16
With intrinsic viscosity is the poly-hexanodioic acid certain herbaceous plants with big flowers diol ester of terminal hydroxy group of 0.30dL/g and the poly-suberic acid hexylene glycol ester of the terminal hydroxy group weighing in 10: 1 by weight that intrinsic viscosity is 0.38dL/g; and be after the xylylene diisocyanate of prepolymer total amount 6.6% places mixer pre-mixing evenly with consumption; directly pass through charging machine; adding the twin screw extruder reaction under nitrogen protection extrudes; granulation or directly through blowing; injection moulding; plastic uptake; calendering technology is processed into corresponding goods; each section of twin screw extruder temperature is: 70 ℃ of feeding sections; 150 ℃ of melt zones; 80 ℃ of discharge ports, raw material is 20 minutes by the time of forcing machine.
The intrinsic viscosity of products therefrom is 1.62dL/g; Fusing point is 73.5 ℃; The tensile strength of film is 25.29MPa, and elongation at break is 523%.
Embodiment 17
With intrinsic viscosity is the poly-hexanodioic acid ethohexadiol ester of terminal hydroxy group of 0.40dL/g and the poly-oxalic acid hexylene glycol ester of the terminal hydroxy group weighing in 1: 10 by weight that intrinsic viscosity is 0.48dL/g; and be after the dicyclohexyl methane diisocyanate of prepolymer total amount 2.2% places mixer pre-mixing evenly with consumption; directly pass through charging machine; adding the twin screw extruder reaction under nitrogen protection extrudes; granulation or directly through blowing; injection moulding; plastic uptake; calendering technology is processed into corresponding goods; each section of twin screw extruder temperature is: 100 ℃ of feeding sections; 160 ℃ of melt zones; 110 ℃ of discharge ports, raw material is 30 minutes by the time of forcing machine.
The intrinsic viscosity of products therefrom is 1.55dL/g; Fusing point is 73.3 ℃; The tensile strength of film is 37.35MPa, and elongation at break is 492%.
Embodiment 18
With intrinsic viscosity is that the terminal hydroxy group polyethylene glycol succinate of 0.11dL/g and terminal hydroxy group polyethylene terephthalate that intrinsic viscosity is 0.15dL/g were by weight weighing in 5: 5; and with consumption be 1 of prepolymer total amount 9.4%; after the 6-hexamethylene diisocyanate places mixer pre-mixing evenly together; directly pass through charging machine; adding the twin screw extruder reaction under nitrogen protection extrudes; granulation or directly through blowing; injection moulding; plastic uptake; calendering technology is processed into corresponding goods; each section of twin screw extruder temperature is: 200 ℃ of feeding sections; 270 ℃ of melt zones; 250 ℃ of discharge ports, raw material is 5 minutes by the time of forcing machine.
The intrinsic viscosity of products therefrom is 0.97dL/g; Fusing point is 174.3 ℃; The tensile strength of film is 53.62MPa, and elongation at break is 117%.
Embodiment 19
With intrinsic viscosity is the poly-suberic acid certain herbaceous plants with big flowers diol ester of terminal hydroxy group of 0.47dL/g and the poly-m-phthalic acid hexylene glycol ester of the terminal hydroxy group weighing in 7: 3 by weight that intrinsic viscosity is 0.50dL/g; and be after the tolylene diisocyanate of prepolymer total amount 0.5% places mixer pre-mixing evenly with consumption; directly pass through charging machine; adding the twin screw extruder reaction under nitrogen protection extrudes; granulation or directly through blowing; injection moulding; plastic uptake; calendering technology is processed into corresponding goods; each section of twin screw extruder temperature is: 200 ℃ of feeding sections; 220 ℃ of melt zones; 210 ℃ of discharge ports, raw material is 30 minutes by the time of forcing machine.
The intrinsic viscosity of products therefrom is 1.39dL/g; Fusing point is 148.2 ℃; The tensile strength of film is 40.48MPa, and elongation at break is 450%.
Embodiment 20
With intrinsic viscosity is the poly-suberic acid certain herbaceous plants with big flowers diol ester of terminal hydroxy group of 0.37dL/g and the poly-phthalic acid hexylene glycol ester of the terminal hydroxy group weighing in 3: 7 by weight that intrinsic viscosity is 0.35dL/g; and be after the tolylene diisocyanate of prepolymer total amount 1.5% places mixer pre-mixing evenly with consumption; directly pass through charging machine; adding the twin screw extruder reaction under nitrogen protection extrudes; granulation or directly through blowing; injection moulding; plastic uptake; calendering technology is processed into corresponding goods; each section of twin screw extruder temperature is: 200 ℃ of feeding sections; 220 ℃ of melt zones; 210 ℃ of discharge ports, raw material is 15 minutes by the time of forcing machine.
The intrinsic viscosity of products therefrom is 1.19dL/g; Fusing point is 158.3 ℃; The tensile strength of film is 55.62MPa, and elongation at break is 350%.
Claims (6)
1. multi-block copolyesters, its general structure is:
In the formula, R represents the hydrocarbyl portion of vulcabond, and x, a, b are 2～10 integer, y, c are 0～8 integer, and during x=b, y ≠ c is during y=c, x ≠ b, j, k, n are the integer greater than 5, and the intrinsic viscosity of this multi-block copolyesters is 0.7～4.7dL/g, and fusing point is 70～240 ℃, tensile strength is 10～67MPa, and elongation at break is 20～1100%.
2. method for preparing the described multi-block copolyesters of claim 1; this method is earlier with prepolymer I and prepolymer II intensification fusion and stirring under protection of inert gas; add vulcabond then; got final product in 5 minutes～10 hours 90～270 ℃ of frit reactions; wherein prepolymer I and prepolymer II count 1～10: 1～10 by weight; the vulcabond consumption counts 0.5～10% by prepolymer I and prepolymer II gross weight; or with prepolymer I; after prepolymer II and vulcabond premix are even; under protection of inert gas, react extruding pelletization or directly make product through forcing machine in 70～270 ℃; the residence time of raw material in forcing machine is 1～30 minute; wherein prepolymer I and prepolymer II count 1～10: 1～10 by weight, and the vulcabond consumption counts 0.5～10% by prepolymer I and prepolymer II gross weight.
3. the preparation method of multi-block copolyesters according to claim 2; it is characterized in that this method is earlier with prepolymer I and prepolymer II intensification fusion and stirring under protection of inert gas; add vulcabond then, got final product in 5 minutes～5 hours 150～270 ℃ of frit reactions.
4. according to the preparation method of claim 2 or 3 described multi-block copolyesters, it is characterized in that prepolymer I used in this method is the terminal hydroxy group aliphatic polyester, its structural formula is:
B is 2～10 integer in the formula, and c is 0～8 integer, and n is the integer greater than 5; Used prepolymer II is terminal hydroxy group aromatic polyester or another kind of terminal hydroxy group aliphatic polyester, and its structural formula is respectively:
A and x are 2～10 integer in the formula, and y is 0～8 integer, and k and j are the integer greater than 5, and used prepolymer II is when being another kind of terminal hydroxy group aliphatic polyester, during x=b in prepolymer I and the prepolymer II structural formula, and y ≠ c, during y=c, x ≠ b.
5. according to the preparation method of claim 2 or 3 described multi-block copolyesters, it is characterized in that vulcabond used in this method is 1, any in 6-hexamethylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate or the dicyclohexyl methane diisocyanate.
6. the preparation method of multi-block copolyesters according to claim 4, it is characterized in that vulcabond used in this method is 1, any in 6-hexamethylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate or the dicyclohexyl methane diisocyanate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010100281007A CN101768246B (en) | 2010-01-15 | 2010-01-15 | Multi-block copolyesters and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010100281007A CN101768246B (en) | 2010-01-15 | 2010-01-15 | Multi-block copolyesters and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101768246A true CN101768246A (en) | 2010-07-07 |
| CN101768246B CN101768246B (en) | 2011-12-07 |
Family
ID=42501364
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010100281007A Active CN101768246B (en) | 2010-01-15 | 2010-01-15 | Multi-block copolyesters and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101768246B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102492119A (en) * | 2011-11-25 | 2012-06-13 | 北京理工大学 | Polyester polyol having block structure and application thereof |
| CN104610522A (en) * | 2015-01-30 | 2015-05-13 | 四川大学 | High-toughness multiblock copolyester elastomer and preparation method thereof |
-
2010
- 2010-01-15 CN CN2010100281007A patent/CN101768246B/en active Active
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102492119A (en) * | 2011-11-25 | 2012-06-13 | 北京理工大学 | Polyester polyol having block structure and application thereof |
| CN102492119B (en) * | 2011-11-25 | 2013-06-12 | 北京理工大学 | Polyester polyol having block structure and application thereof |
| CN104610522A (en) * | 2015-01-30 | 2015-05-13 | 四川大学 | High-toughness multiblock copolyester elastomer and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101768246B (en) | 2011-12-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP3445800B1 (en) | New polyester and compositions containing it | |
| CN109438682B (en) | Copolyester, preparation method and product thereof | |
| CN101024696A (en) | Polylactic-acid block copolymer and its preparing method | |
| CN111205603B (en) | Biodegradable mulching film and preparation method thereof | |
| Hahm et al. | Bench-Scale Synthesis and Characterization of Biodegradable Aliphatic–Aromatic Random Copolymers with 1, 4-Cyclohexanedimethanol Units Toward Sustainable Packaging Applications | |
| CN101768246B (en) | Multi-block copolyesters and preparation method thereof | |
| CN113817148B (en) | Polylactic acid copolymer, preparation method and application thereof, and preparation method of blend film | |
| CN104610522B (en) | A kind of high tenacity multiblock ester elastomer and preparation method thereof | |
| KR101792080B1 (en) | Manufacturing method of elution type knitted fabric | |
| CN101096415B (en) | Poly(P-dioxanone) and preparation method thereof | |
| CN110591058A (en) | Method for catalytic polycondensation of degradable packaging material | |
| CN115109237B (en) | Continuous preparation process of aliphatic degradable polyester | |
| CN115010908B (en) | Preparation method of biodegradable low-melting-point hot-melt polyester | |
| CN115558092A (en) | Recycling method of waste PET and biodegradable copolyester prepared by adopting recycling method | |
| CN103910858A (en) | Synthesis method of biodegradable copolyester | |
| CN110776628B (en) | Preparation method of bio-based full-biodegradable copolyester | |
| CN102863626B (en) | Biomass modified polymer and preparation method and application thereof | |
| CN115703923B (en) | Toughened polylactic acid material and preparation method and application thereof | |
| CN115725062B (en) | Bio-based copolyester material and preparation method thereof | |
| CN114181654B (en) | Biodegradable copolyester hot melt adhesive and preparation method thereof | |
| CN111777753B (en) | Heat-resistant flame-retardant polyester, polyester product, preparation method and application thereof | |
| KR20220073091A (en) | Method of preparing eco-friendly polyester and eco-friendly polyester prepared by the method | |
| CN115160742A (en) | PBAT composite material and preparation method thereof | |
| CN118085257A (en) | Mesoporous silica containing titanium and tin, and preparation method and application thereof | |
| CN111979590A (en) | Biodegradable alcohol modified copolyester wool top and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |