CN105348501A - Bisoxazoline chain-extending polylactic acid polyhydric alcohol with low-acid value and preparation method for bisoxazoline chain-extending polylactic acid polyhydric alcohol with low-acid value - Google Patents
Bisoxazoline chain-extending polylactic acid polyhydric alcohol with low-acid value and preparation method for bisoxazoline chain-extending polylactic acid polyhydric alcohol with low-acid value Download PDFInfo
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Abstract
The invention provides a preparation method for bisoxazoline chain-extending polylactic acid polyhydric alcohol with low-acid value. The preparation method comprises the steps of: S1, preparing polylactic acid with the theoretical molecular weight of 500-4000 and the acid value of 3.50-14.10; and S2, adding bisoxazoline into the polylactic acid for heating reaction under protection of nitrogen or inert gas to obtain the polylactic acid polyhydric alcohol with the acid value of being less than or equal to 3. The invention further provides the bisoxazoline chain-extending polylactic acid polyhydric alcohol with low-acid value prepared by virtue of the preparation method.
Description
Technical field
The present invention relates to a kind of preparation method of low acid number polylactic acid multi-element alcohol, two oxazoline chain extension polylactic acid multi-element alcohol of especially a kind of low acid number and preparation method thereof.
Background technology
Polyester polyol is the main raw material preparing polyurethane material, can be used for preparing the materials such as polyurethane elastomer, coating, tackiness agent, rubber, foam.Existing polyester polyol is formed by diprotic acid and polyol condensating usually.And the raw material such as diprotic acid and polyvalent alcohol comes from petroleum products substantially, along with the consumption day by day of petroleum resources, renewable resources is utilized to substitute to need the consume petroleum polyester polyol of resource to be more and more subject to people's attention to produce polyurethane material.
Polylactic acid multi-element alcohol is for monomer synthesize raw material with microbial fermentation product lactic acid, it has nontoxic nonirritant, the characteristics such as good biocompatibility and degradation property, it is desirable resin additive, properties-correcting agent, can be used to prepare biodegradable polyurethane material, alternative polyester polyol prepares polyurethane material.
But traditional polylactic acid multi-element alcohol is prepared by acid through direct polycondensation by lactic or by rac-Lactide ring-opening polymerization usually.Owing to there is the side reactions such as oxidation and cracking in polycondensation or polymerization process, containing more end carboxyl poly(lactic acid) in the polylactic acid multi-element alcohol prepared by aforesaid method, make the acid number of polylactic acid multi-element alcohol higher, thus reduce the reactivity worth of polylactic acid multi-element alcohol.
Summary of the invention
In order to overcome defect of the prior art, the invention provides the preparation method of the good polylactic acid multi-element alcohol of a kind of low acid number, reactivity worth.
Object of the present invention is achieved through the following technical solutions:
A preparation method for the two oxazoline chain extension polylactic acid multi-element alcohol of low acid number, it comprises the steps: S1: prepare theoretical molecular for 500 ~ 4000, acid number is the poly(lactic acid) of 3.50 ~ 14.10; S2: two oxazoline is joined described poly(lactic acid) carry out reacting by heating under nitrogen or protection of inert gas, obtains the polylactic acid multi-element alcohol that acid number is less than or equal to 3.
The preparation method of described poly(lactic acid) comprises: by acid through direct polycondensation by lactic, by rac-Lactide ring-opening polymerization, causes lactic acid mass polymerization by polyvalent alcohol.
The preparation method of described poly(lactic acid) is as follows: add 1 of 6.63 ~ 70.32 weight parts; 4-butyleneglycol, the rac-Lactide of 216.02 ~ 432.67 weight parts, the catalyzer of 0.11 ~ 0.60 weight part; stir under nitrogen protection and be warming up to 135 ~ 175 DEG C, react 4 ~ 28 hours at 135 ~ 175 DEG C.
Described catalyzer is a kind of in iron(ic) chloride, aluminum chloride, butyllithium, sodium alkoxide, potassium alcoholate stannous octoate, tin tetrachloride, tin protochloride, stannous acetate, stannic oxide or their arbitrary combination.
The weight ratio of described pair of oxazoline and described poly(lactic acid) is 1.02 ~ 6.84:50.51 ~ 288.02.
Described step S2 comprises the steps: described pair of oxazoline and poly(lactic acid) to stir raised temperature to 140 ~ 165 DEG C further under nitrogen protection condition; react 0.5 ~ 4.0 hour at 140 ~ 165 DEG C, until obtain the low acid number polylactic acid multi-element alcohol that acid number is 0.99 ~ 1.50.
Described pair of oxazoline is 2,2'-(1,3-phenylene)-bisoxazoline, 2,2-(1,4-phenylene) bisoxazoline, 2, wherein a kind of such as 6-bis-[(4S)-4-tertiary butyl-2-oxazoline group] pyridine, 2,6-bis-[(4R)-4-phenyl-2-oxazoline group] pyridine or their arbitrary combination.
A preparation method for the two oxazoline chain extension polylactic acid multi-element alcohol of low acid number, it is reacted with two oxazoline by poly(lactic acid) and obtains, and the chemical equation of this reaction is as follows:
Wherein, described R comprises ether, alkyl.
The chemical equation preparing described poly(lactic acid) is as follows:
Wherein, described catalyzer is a kind of in iron(ic) chloride, aluminum chloride, butyllithium, sodium alkoxide, potassium alcoholate stannous octoate, tin tetrachloride, tin protochloride, stannous acetate, stannic oxide or their arbitrary combination.
Compared with prior art, the present invention is by synthesis path reasonable in design, the poly(lactic acid) of certain acid number and theoretical molecular is selected to be obtained by reacting polylactic acid multi-element alcohol with two oxazoline, modification has been carried out to the end position of polylactic acid multi-element alcohol, reduce the content of end carboxyl, thus obtain the polylactic acid multi-element alcohol that acid number is less than or equal to 3.Enhance the reactivity of polylactic acid multi-element alcohol, be conducive to polylactic acid multi-element alcohol in subsequent applications process, participate in reaction, such as, when preparing polyurethane material, the epoxide modified polylactic acid multi-element alcohol in low acid number end position is easier to and isocyanate reaction.In addition, preparation method of the present invention also has that technique is simple, production cost is low, preparation process does not need solvent, three-waste free discharge, and having can the feature such as scale operation.The present invention also provides a kind of low acid number prepared by aforesaid method two oxazoline chain extension polylactic acid multi-element alcohol.
Embodiment
Below in conjunction with specific embodiment, the present invention is more specifically described in detail, but embodiments of the present invention are not limited thereto, for the processing parameter do not indicated especially, can refer to routine techniques and carry out.
A preparation method for the two oxazoline chain extension polylactic acid multi-element alcohol of low acid number, it comprises the steps:
S1: prepare theoretical molecular for 500 ~ 4000, acid number is the poly(lactic acid) of 3.50 ~ 14.10;
S2: two oxazoline is joined described poly(lactic acid) carry out reacting by heating under nitrogen or protection of inert gas, obtains the polylactic acid multi-element alcohol that acid number is less than or equal to 3.
In step sl, the preparation method of described poly(lactic acid) does not limit, and can comprise by acid through direct polycondensation by lactic method, causes lactic acid mass polymerization by rac-Lactide ring-opening polymerization method and by polyvalent alcohol.Preferably, described poly(lactic acid) is polymerized by rac-Lactide ring-opening polymerization method, and its chemical equation is:
Described catalyzer is wherein a kind of such as iron(ic) chloride, aluminum chloride, butyllithium, sodium alkoxide, potassium alcoholate stannous octoate, tin tetrachloride, tin protochloride, stannous acetate, stannic oxide or their arbitrary combination.
Preferably; the preparation method of described poly(lactic acid) is as follows: add 1 of 6.63 ~ 70.32 weight parts; 4-butyleneglycol; the rac-Lactide of 216.02 ~ 432.67 weight parts; the catalyzer of 0.11 ~ 0.60 weight part; stir under nitrogen protection and be warming up to 135 ~ 175 DEG C, react 4 ~ 28 hours at 135 ~ 175 DEG C.
In step s 2, be mainly used in carrying out the modification of end position to described poly(lactic acid), particularly, in described poly(lactic acid), add two oxazoline modification is carried out to it.The weight ratio of described epoxy compounds and described poly(lactic acid) is 1.02 ~ 6.84:50.51 ~ 288.02.Its chemical equation is:
Wherein, the R in described epoxy compounds is generally containing alkyl or ehter bond.Preferably, described pair of oxazoline is 2,2'-(1,3-phenylene)-bisoxazoline, 2,2-(1,4-phenylene) wherein a kind of such as bisoxazoline, 2,6-bis-[(4S)-4-tertiary butyl-2-oxazoline group] pyridine, 2,6-bis-[(4R)-4-phenyl-2-oxazoline group] pyridine or their arbitrary combination.Described step S2 can comprise the steps: described pair of oxazoline and poly(lactic acid) to stir raised temperature to 140 ~ 165 DEG C further under nitrogen protection condition; react 0.5 ~ 4.0 hour at 140 ~ 165 DEG C, until obtain the low acid number polylactic acid multi-element alcohol that acid number is 0.99 ~ 1.50.
Present invention also offers two its acid number of oxazoline chain extension polylactic acid multi-element alcohol of a kind of low acid number and be less than or equal to 3.Preferably, its acid number is 0.99 ~ 1.50.
Be appreciated that, the present invention is by synthesis path reasonable in design, the poly(lactic acid) of certain acid number and theoretical molecular is selected to be obtained by reacting polylactic acid multi-element alcohol with two oxazoline, modification has been carried out to the end position of polylactic acid multi-element alcohol, reduce the content of end carboxyl, thus obtain the polylactic acid multi-element alcohol that acid number is less than or equal to 3.Enhance the reactivity of polylactic acid multi-element alcohol, be conducive to polylactic acid multi-element alcohol in subsequent applications process, participate in reaction, such as, when preparing polyurethane material, the epoxide modified polylactic acid multi-element alcohol in low acid number end position is easier to and isocyanate reaction.In addition, preparation method of the present invention also has that technique is simple, production cost is low, preparation process does not need solvent, three-waste free discharge, and having can the feature such as scale operation.
The polylactic acid multi-element alcohol method epoxide modified to low acid number end position of the present invention below in conjunction with specific embodiment is described.
Embodiment 1
A preparation method for low acid number polylactic acid multi-element alcohol, it comprises the following steps (following number is weight part):
Theoretical molecular is the preparation of the poly(lactic acid) of 500: in round-bottomed flask, add 47.20g1; 4-butyleneglycol; 216.02g rac-Lactide; 0.11g stannous octoate; vacuumize and use nitrogen replacement 3 times; constantly stir under nitrogen protection and be warming up to 140 DEG C, react 24 hours at 140 DEG C, can obtain that 261.56g theoretical molecular is 500, acid number is the poly(lactic acid) of 3.50.
The modification of poly(lactic acid): add the poly(lactic acid) that 70.32g aforesaid method is obtained in round-bottomed flask; 1.02g2; 2'-(1; 3-phenylene)-bisoxazoline; vacuumize and use nitrogen replacement 3 times; under nitrogen protection condition, constantly stir raised temperature to 140 DEG C, react 1.0 hours at 140 DEG C, the low acid number polylactic acid multi-element alcohol that acid number is 0.99 can be obtained.
Embodiment 2
A preparation method for low acid number polylactic acid multi-element alcohol, it comprises the following steps (following number is weight part):
Theoretical molecular is the preparation of the poly(lactic acid) of 1000: in round-bottomed flask, add 28.40g1; 4-butyleneglycol; 288.65g rac-Lactide; 0.14g stannous octoate; vacuumize and use nitrogen replacement 3 times; constantly stir under nitrogen protection and be warming up to 140 DEG C, react 24 hours at 140 DEG C, can obtain that 301.33g theoretical molecular is 1000, acid number is the poly(lactic acid) of 4.00.
The modification of poly(lactic acid): add the poly(lactic acid) that 52.20g aforesaid method is obtained in round-bottomed flask; 1.48g2; 2'-(1; 3-phenylene)-bisoxazoline; vacuumize and use nitrogen replacement 3 times; under nitrogen protection condition, constantly stir raised temperature to 165 DEG C, react 1.5 hours at 165 DEG C, the low acid number polylactic acid multi-element alcohol that acid number is 1.40 can be obtained.
Embodiment 3
A preparation method for low acid number polylactic acid multi-element alcohol, it comprises the following steps (following number is weight part):
Theoretical molecular is the preparation of the poly(lactic acid) of 2000: in round-bottomed flask, add 12.27g1; 4-butyleneglycol; 288.64g rac-Lactide; 0.14g stannous octoate; vacuumize and use nitrogen replacement 3 times; constantly stir under nitrogen protection and be warming up to 140 DEG C, react 24 hours at 140 DEG C, can obtain that 273.45g theoretical molecular is 2000, acid number is the poly(lactic acid) of 4.50.
The modification of poly(lactic acid): add the poly(lactic acid) that 50.34g aforesaid method is obtained in round-bottomed flask; then 2.76g2 is added; 2'-(1; 3-phenylene)-bisoxazoline; vacuumize and use nitrogen replacement 3 times; under nitrogen protection condition, constantly stir raised temperature to 145 DEG C, react 1.5 hours at 145 DEG C, the low acid number polylactic acid multi-element alcohol that acid number is 1.24 can be obtained.
Embodiment 4
A preparation method for low acid number polylactic acid multi-element alcohol, it comprises the following steps (following number is weight part):
Theoretical molecular is the preparation of the poly(lactic acid) of 3000: in round-bottomed flask, add 13.35g1; 4-butyleneglycol; 432.67g rac-Lactide; 0.22g stannous octoate; vacuumize and use nitrogen replacement 3 times; constantly stir under nitrogen protection and be warming up to 140 DEG C, react 24 hours at 140 DEG C, can obtain that 438.33g theoretical molecular is 3000, acid number is the poly(lactic acid) of 3.60.
The modification of poly(lactic acid): add the poly(lactic acid) that 50.51g aforesaid method is obtained in round-bottomed flask; 3.54g2; 2'-(1; 3-phenylene)-bisoxazoline; vacuumize and use nitrogen replacement 3 times; under nitrogen protection condition, constantly stir raised temperature to 150 DEG C, react 1.5 hours at 150 DEG C, the low acid number polylactic acid multi-element alcohol that acid number is 1.50 can be obtained.
Embodiment 5
A preparation method for low acid number polylactic acid multi-element alcohol, it comprises the following steps (following number is weight part):
Theoretical molecular is the preparation of the poly(lactic acid) of 4000: in round-bottomed flask, add 6.63g1; 4-butyleneglycol; 288.00g rac-Lactide; 0.60g stannous octoate; vacuumize and use nitrogen replacement 3 times; constantly stir under nitrogen protection and be warming up to 140 DEG C, react 24 hours at 140 DEG C, can obtain that 275.34g theoretical molecular is 4000, acid number is the poly(lactic acid) of 14.10.
The modification of poly(lactic acid): add the poly(lactic acid) that 51.56g aforesaid method is obtained in round-bottomed flask; 6.84g2; 2'-(1; 3-phenylene)-bisoxazoline; vacuumize and use nitrogen replacement 3 times; under nitrogen protection condition, constantly stir raised temperature to 155 DEG C, react 2.0 hours at 155 DEG C, the low acid number polylactic acid multi-element alcohol that acid number is 1.48 can be obtained.
Embodiment 6
A preparation method for low acid number polylactic acid multi-element alcohol, it comprises the following steps (following number is weight part):
Theoretical molecular is the preparation of the poly(lactic acid) of 4000: in round-bottomed flask, add 6.51g1; 4-butyleneglycol; 285.20g rac-Lactide; 0.29g iron(ic) chloride; vacuumize and use nitrogen replacement 3 times; constantly stir under nitrogen protection and be warming up to 135 DEG C, react 4 hours at 135 DEG C, can obtain that 289.20g theoretical molecular is 4000, acid number is the poly(lactic acid) of 8.62.
The modification of poly(lactic acid): add the poly(lactic acid) that 52.01g aforesaid method is obtained in round-bottomed flask; 3.67g2; 2'-(1; 3-phenylene)-bisoxazoline; vacuumize and use nitrogen replacement 3 times; under nitrogen protection condition, constantly stir raised temperature to 140 DEG C, react 1.0 hours at 140 DEG C, the low acid number polylactic acid multi-element alcohol that acid number is 1.24 can be obtained.
Embodiment 7
A preparation method for low acid number polylactic acid multi-element alcohol, it comprises the following steps (following number is weight part):
Theoretical molecular is the preparation of the poly(lactic acid) of 3000: in round-bottomed flask, add 13.42g1; 4-butyleneglycol; 434.83g rac-Lactide; 0.46g aluminum chloride; vacuumize and use nitrogen replacement 3 times; constantly stir under nitrogen protection and be warming up to 150 DEG C, react 12 hours at 150 DEG C, can obtain that 445.59g theoretical molecular is 3000, acid number is the poly(lactic acid) of 6.53.
The modification of poly(lactic acid): add the poly(lactic acid) that 50.26g aforesaid method is obtained in round-bottomed flask; 3.28g2; 2'-(1; 3-phenylene)-bisoxazoline; vacuumize and use nitrogen replacement 3 times; under nitrogen protection condition, constantly stir raised temperature to 155 DEG C, react 3.5 hours at 155 DEG C, the low acid number polylactic acid multi-element alcohol that acid number is 1.38 can be obtained.
Embodiment 8
A preparation method for low acid number polylactic acid multi-element alcohol, it comprises the following steps (following number is weight part):
Theoretical molecular is the preparation of the poly(lactic acid) of 4000: in round-bottomed flask, add 6.58g1; 4-butyleneglycol; 288.20g rac-Lactide; 0.28g butyllithium; vacuumize and use nitrogen replacement 3 times; constantly stir under nitrogen protection and be warming up to 175 DEG C, react 28 hours at 175 DEG C, can obtain that 292.50g theoretical molecular is 4000, acid number is the poly(lactic acid) of 6.53.
The modification of poly(lactic acid): add the poly(lactic acid) that 50.46g aforesaid method is obtained in round-bottomed flask; 5.89g2; 2'-(1; 3-phenylene)-bisoxazoline; vacuumize and use nitrogen replacement 3 times; under nitrogen protection condition, constantly stir raised temperature to 165 DEG C, react 4.0 hours at 165 DEG C, the low acid number polylactic acid multi-element alcohol that acid number is 1.39 can be obtained.
Embodiment 9
A preparation method for low acid number polylactic acid multi-element alcohol, it comprises the following steps (following number is weight part):
Theoretical molecular is the preparation of the poly(lactic acid) of 2000: in round-bottomed flask, add 12.46g1; 4-butyleneglycol; 288.46g rac-Lactide; 0.37g sodium alkoxide; vacuumize and use nitrogen replacement 3 times; constantly stir under nitrogen protection and be warming up to 168 DEG C, react 18 hours at 168 DEG C, can obtain that 294.45g theoretical molecular is 2000, acid number is the poly(lactic acid) of 10.46.
The modification of poly(lactic acid): add the poly(lactic acid) that 50.43g aforesaid method is obtained in round-bottomed flask; 4.56g2; 2'-(1; 3-phenylene)-bisoxazoline; vacuumize and use nitrogen replacement 3 times; under nitrogen protection condition, constantly stir raised temperature to 158 DEG C, react 3.5 hours at 158 DEG C, the low acid number polylactic acid multi-element alcohol that acid number is 1.45 can be obtained.
Embodiment 10
A preparation method for low acid number polylactic acid multi-element alcohol, it comprises the following steps (following number is weight part):
Theoretical molecular is the preparation of the poly(lactic acid) of 2000: in round-bottomed flask, add 12.76g1; 4-butyleneglycol; 288.43g rac-Lactide; 0.24g potassium alcoholate stannous octoate; vacuumize and use nitrogen replacement 3 times; constantly stir under nitrogen protection and be warming up to 148 DEG C, react 20 hours at 148 DEG C, can obtain that 297.46g theoretical molecular is 2000, acid number is the poly(lactic acid) of 7.23.
The modification of poly(lactic acid): add the poly(lactic acid) that 50.49g aforesaid method is obtained in round-bottomed flask; 5.43g2; 2'-(1; 3-phenylene)-bisoxazoline; vacuumize and use nitrogen replacement 3 times; under nitrogen protection condition, constantly stir raised temperature to 150 DEG C, react 2.5 hours at 150 DEG C, the low acid number polylactic acid multi-element alcohol that acid number is 1.46 can be obtained.
Embodiment 11
A preparation method for low acid number polylactic acid multi-element alcohol, it comprises the following steps (following number is weight part):
Theoretical molecular is the preparation of the poly(lactic acid) of 2000: in round-bottomed flask, add 12.76g1; 4-butyleneglycol; 288.31g rac-Lactide; 0.25g tin tetrachloride; vacuumize and use nitrogen replacement 3 times; constantly stir under nitrogen protection and be warming up to 165 DEG C, react 6 hours at 165 DEG C, can obtain that 294.43g theoretical molecular is 2000, acid number is the poly(lactic acid) of 6.13.
The modification of poly(lactic acid): add the poly(lactic acid) that 50.37g aforesaid method is obtained in round-bottomed flask; 4.76g2; 2'-(1; 3-phenylene)-bisoxazoline; vacuumize and use nitrogen replacement 3 times; under nitrogen protection condition, constantly stir raised temperature to 152 DEG C, react 3.0 hours at 152 DEG C, the low acid number polylactic acid multi-element alcohol that acid number is 1.08 can be obtained.
Embodiment 12
A preparation method for low acid number polylactic acid multi-element alcohol, it comprises the following steps (following number is weight part):
Theoretical molecular is the preparation of the poly(lactic acid) of 2000: in round-bottomed flask, add 12.39g1; 4-butyleneglycol; 288.43g rac-Lactide; 0.37g tin protochloride; vacuumize and use nitrogen replacement 3 times; constantly stir under nitrogen protection and be warming up to 165 DEG C, react 6 hours at 165 DEG C, can obtain that 298.49g theoretical molecular is 2000, acid number is the poly(lactic acid) of 9.48.
The modification of poly(lactic acid): add the poly(lactic acid) that 50.47g aforesaid method is obtained in round-bottomed flask; 4.65g2; 2-(1; 4-phenylene) bisoxazoline; vacuumize and use nitrogen replacement 3 times; under nitrogen protection condition, constantly stir raised temperature to 152 DEG C, react 3.6 hours at 152 DEG C, the low acid number polylactic acid multi-element alcohol that acid number is 1.37 can be obtained.
Embodiment 13
A preparation method for low acid number polylactic acid multi-element alcohol, it comprises the following steps (following number is weight part):
Theoretical molecular is the preparation of the poly(lactic acid) of 2000: in round-bottomed flask, add 12.79g1; 4-butyleneglycol; 288.56g rac-Lactide; 0.25g stannous acetate; vacuumize and use nitrogen replacement 3 times; constantly stir under nitrogen protection and be warming up to 172 DEG C, react 20 hours at 172 DEG C, can obtain that 298.43g theoretical molecular is 2000, acid number is the poly(lactic acid) of 9.74.
The modification of poly(lactic acid): add the poly(lactic acid) that 50.15g aforesaid method is obtained in round-bottomed flask; 4.86g2; 2-(1; 4-phenylene) bisoxazoline; vacuumize and use nitrogen replacement 3 times; under nitrogen protection condition, constantly stir raised temperature to 162 DEG C, react 3.6 hours at 162 DEG C, the low acid number polylactic acid multi-element alcohol that acid number is 1.35 can be obtained.
Embodiment 14
A preparation method for low acid number polylactic acid multi-element alcohol, it comprises the following steps (following number is weight part):
Theoretical molecular is the preparation of the poly(lactic acid) of 2000: in round-bottomed flask, add 12.94g1; 4-butyleneglycol; 288.47g rac-Lactide; 0.27g stannic oxide; vacuumize and use nitrogen replacement 3 times; constantly stir under nitrogen protection and be warming up to 150 DEG C, react 20 hours at 150 DEG C, can obtain that 297.46g theoretical molecular is 2000, acid number is the poly(lactic acid) of 5.78.
The modification of poly(lactic acid): add the poly(lactic acid) that 50.70g aforesaid method is obtained in round-bottomed flask; 5.44g2; 6-bis-[(4S)-4-tertiary butyl-2-oxazoline group] pyridine; vacuumize with and nitrogen replacement 3 times; constantly raised temperature to 155 DEG C is stirred under nitrogen protection condition; react 4.0 hours at 155 DEG C, the low acid number polylactic acid multi-element alcohol that acid number is 1.24 can be obtained.
The explanation of above embodiment just understands method of the present invention and core concept thereof for helping.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improve and modify and also fall in the protection domain of the claims in the present invention.Be apparent for those skilled in the art to the multiple amendment of these embodiments, General Principle as defined herein can realize without departing from the spirit or scope of the present invention in other embodiments.Therefore, the present invention can not be restricted to these embodiments shown in this article, but will meet the widest scope consistent with principle disclosed herein and features of novelty.
Claims (10)
1. a preparation method for the two oxazoline chain extension polylactic acid multi-element alcohol of low acid number, it comprises the steps:
S1: prepare theoretical molecular for 500 ~ 4000, acid number is the poly(lactic acid) of 3.50 ~ 14.10;
S2: two oxazoline is joined described poly(lactic acid) carry out reacting by heating under nitrogen or protection of inert gas, obtains the polylactic acid multi-element alcohol that acid number is less than or equal to 3.
2. the preparation method of the two oxazoline chain extension polylactic acid multi-element alcohol of low acid number according to claim 1, it is characterized in that, the preparation method of described poly(lactic acid) comprises: by acid through direct polycondensation by lactic, by rac-Lactide ring-opening polymerization, causes lactic acid mass polymerization by polyvalent alcohol.
3. the preparation method of the two oxazoline chain extension polylactic acid multi-element alcohol of low acid number according to claim 2; it is characterized in that; the preparation method of described poly(lactic acid) is as follows: add 1 of 6.63 ~ 70.32 weight parts; 4-butyleneglycol; the rac-Lactide of 216.02 ~ 432.67 weight parts; the catalyzer of 0.11 ~ 0.60 weight part, stirs under nitrogen protection and is warming up to 135 ~ 175 DEG C, react 4 ~ 28 hours at 135 ~ 175 DEG C.
4. the preparation method of the two oxazoline chain extension polylactic acid multi-element alcohol of low acid number according to claim 3, it is characterized in that, described catalyzer is one in iron(ic) chloride, aluminum chloride, butyllithium, sodium alkoxide, potassium alcoholate stannous octoate, tin tetrachloride, tin protochloride, stannous acetate, stannic oxide or arbitrary combination.
5. the preparation method of the two oxazoline chain extension polylactic acid multi-element alcohol of low acid number according to claim 1, it is characterized in that, the weight ratio of described pair of oxazoline and described poly(lactic acid) is 1.02 ~ 6.84:50.51 ~ 288.02.
6. the preparation method of the two oxazoline chain extension polylactic acid multi-element alcohol of low acid number according to claim 5; it is characterized in that; described step S2 comprises the steps: described pair of oxazoline and poly(lactic acid) to stir raised temperature to 140 ~ 165 DEG C further under nitrogen protection condition; react 0.5 ~ 4.0 hour at 140 ~ 165 DEG C, until obtain the low acid number polylactic acid multi-element alcohol that acid number is 0.99 ~ 1.50.
7. the preparation method of the two oxazoline chain extension polylactic acid multi-element alcohol of the low acid number according to claim 1 any one, it is characterized in that, described pair of oxazoline is 2,2'-(1,3-phenylene)-bisoxazoline, 2,2-(Isosorbide-5-Nitrae-phenylene) bisoxazoline, 2, wherein a kind of such as 6-bis-[(4S)-4-tertiary butyl-2-oxazoline group] pyridine, 2,6-bis-[(4R)-4-phenyl-2-oxazoline group] pyridine or their arbitrary combination.
8. a preparation method for the two oxazoline chain extension polylactic acid multi-element alcohol of low acid number, is characterized in that, it is reacted with two oxazoline by poly(lactic acid) and obtains, and the chemical equation of this reaction is as follows:
Wherein, described R comprises ether, alkyl.
9. the preparation method of the two oxazoline chain extension polylactic acid multi-element alcohol of low acid number according to claim 1, it is characterized in that, the chemical equation preparing described poly(lactic acid) is as follows:
Wherein, described catalyzer is one in iron(ic) chloride, aluminum chloride, butyllithium, sodium alkoxide, potassium alcoholate stannous octoate, tin tetrachloride, tin protochloride, stannous acetate, stannic oxide or arbitrary combination.
10. one kind with the two oxazoline chain extension polylactic acid multi-element alcohol of low acid number prepared by the preparation method of the two oxazoline chain extension polylactic acid multi-element alcohol of the low acid number described in claim 1-9, it is characterized in that, the acid number of the two oxazoline chain extension polylactic acid multi-element alcohol of this low acid number is less than or equal to 3.
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| CN201510504687.7A CN105348501A (en) | 2015-08-17 | 2015-08-17 | Bisoxazoline chain-extending polylactic acid polyhydric alcohol with low-acid value and preparation method for bisoxazoline chain-extending polylactic acid polyhydric alcohol with low-acid value |
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| CN201510504687.7A CN105348501A (en) | 2015-08-17 | 2015-08-17 | Bisoxazoline chain-extending polylactic acid polyhydric alcohol with low-acid value and preparation method for bisoxazoline chain-extending polylactic acid polyhydric alcohol with low-acid value |
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| CN113388097A (en) * | 2021-06-21 | 2021-09-14 | 泰喜医疗科技(苏州)有限公司 | Synthesis method of high-stability polyglycolide |
| CN115850988A (en) * | 2022-12-30 | 2023-03-28 | 科派股份有限公司 | Polylactic acid environment-friendly board for furniture manufacturing and furniture manufactured by polylactic acid environment-friendly board |
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| CN113388097A (en) * | 2021-06-21 | 2021-09-14 | 泰喜医疗科技(苏州)有限公司 | Synthesis method of high-stability polyglycolide |
| CN115850988A (en) * | 2022-12-30 | 2023-03-28 | 科派股份有限公司 | Polylactic acid environment-friendly board for furniture manufacturing and furniture manufactured by polylactic acid environment-friendly board |
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