CN107840949A - A kind of preparation method based on organic-silicon-modified PGA - Google Patents
A kind of preparation method based on organic-silicon-modified PGA Download PDFInfo
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- CN107840949A CN107840949A CN201711031757.7A CN201711031757A CN107840949A CN 107840949 A CN107840949 A CN 107840949A CN 201711031757 A CN201711031757 A CN 201711031757A CN 107840949 A CN107840949 A CN 107840949A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/695—Polyesters containing atoms other than carbon, hydrogen and oxygen containing silicon
- C08G63/6952—Polyesters containing atoms other than carbon, hydrogen and oxygen containing silicon derived from hydroxycarboxylic acids
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/445—Block-or graft-polymers containing polysiloxane sequences containing polyester sequences
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- Polyesters Or Polycarbonates (AREA)
- Silicon Polymers (AREA)
Abstract
The invention discloses a kind of preparation method based on organic-silicon-modified PGA, mixed in the presence of an organic with glycolide from the polysiloxane oligomers of difunctional end-blocking, it is copolymerized under catalyst action, PGA polysiloxane block copolymers, i.e., described organic-silicon-modified PGA is made.Compared with PGA, the block copolymer has the characteristics such as pliability is good, impact resistance is good, heat resistance is good, can apply in 3D printing technique field, rapidly and efficiently baroque product is made, for fields such as bioengineering.
Description
Technical field
The present invention relates to polymeric material field, and in particular to a kind of preparation side based on organic-silicon-modified PGA
Method.
Background technology
Since twentieth century, with the development of science and technology, increasing plastic products are manufactured, us have been given with next life
It is living convenient simultaneously as it largely brings serious " white pollution " for non-degradable material, consequently also great shadow
Ring the physical and mental health of the mankind.Therefore development Biodegradable material is extremely urgent.PGA (PGA) be also known as polyglycolic acid or
Polyglycolic acid, is a kind of important green material with biodegradability, and its synthesis mainly has hydroxyacetic acid directly to contract
Close polymerization and two kinds of the ring-opening polymerisation method of glycolide.It is in engineering plastics and (such as packaging for foodstuff, medicine of biological medicine application field
Thing conveying, biomaterial scaffolds, operation suture thread etc.) aspect have a wide range of applications.
There is very strong crystallizing power yet with PGA, and fusing point is high, causes thermoforming processing temperature high, and it is too high
Processing temperature can make the quick thermal degradation of PGA, cause drastically reducing for intensity, thus significantly limit its extensive use.
In order to improve the application performance of PGA, people have carried out many researchs.Chinese patent (publication number CN105801817A) is public
Open a kind of using salen aluminium as catalyst preparation lactide and the copolymerization process of 6-caprolactone.Chinese patent (publication number
CN104066459A 6-caprolactone and the preparation method to dioxanone block copolymer) are disclosed.Chinese patent is (open
Number CN106986984A) disclose a kind of preparation method of biodegradable poly- (glycolide-ε-caprolactone) block copolymer.China
A kind of polylactide of patent (publication number CN107227507A) and poly (glycolide-lactide) composite fibre, its preparation method, purposes and hand
Art suture.But modification PLA and the PGA material that above-mentioned patent is related to are examined merely from improvement its intensity and processing characteristics etc. mostly
Consider, the PGA that do not have clear improvement pliability and heat resistance.
The content of the invention
The present invention is poor compared with strong, poor toughness, heat endurance on PGA material fragility in the prior art in order to overcome
The problems such as, there is provided a kind of preparation method based on organic-silicon-modified PGA, using chemical modification method, prepare poly- second and hand over
Ester-polydimethylsiloxaneblock block copolymers, compared with PGA, the block copolymer has that pliability is good, impact resistance
The good, characteristic such as heat resistance is good.
To achieve these goals, the present invention uses following technical scheme：
A kind of preparation method based on organic-silicon-modified PGA, had from the polysiloxane oligomers of difunctional end-blocking
Mix with glycolide in the presence of solvent, be copolymerized under catalyst action, PGA-polysiloxane block copolymerization is made
Thing, i.e., described organic-silicon-modified PGA.Compared with PGA, the block copolymer has that pliability is good, impact resistance
The good, characteristic such as heat resistance is good, can apply in 3D printing technique field, rapidly and efficiently baroque product is made.
Preferably, preparation method is following steps：
(1) agent of difunctional siloxane blocking and octamethylcy-clotetrasiloxane are mixed, heat up and stir under 200~1000Pa,
Add catalyst A and carry out ring-opening polymerization, wait to be warming up to more than 140 DEG C, low-boiling-point substance is removed under 50~150Pa and obtains difunctionality
The dimethyl silicone polymer of group's end-blocking；Reaction is carried out in four-neck flask；
(2) nitrogen is passed through in the dimethyl silicone polymer described in step (1) and excludes air, glycolide is added, organic molten
Added in the presence of agent and react 12~36h under catalyst B, 60~200Pa in 130~170 DEG C of oil baths, purified after being cooled to room temperature
Obtain the PGA-poly organo alkyl copolymer.
Preferably, the difunctional siloxane blocking agent described in step (1) is double (the 3- aminopropyls) -1,1 of 1,3-,
Double (the 2- amino-ethyls) -1 of 3,3- tetramethyl disiloxanes, 1,3-, one or both of 1,3,3- tetramethyl disiloxane, or
Person is 1,3- bis (3-hydroxypropyl) -1,1,3,3- tetramethyl disiloxanes, double (2- the ethoxys) -1,1,3,3- tetramethyls two of 1,3-
One or both of siloxanes.
Preferably, the agent of difunctional siloxane blocking and D4 mass ratio are 1 in step (1):100~1:1.More preferably
Mass ratio for the agent of difunctional siloxane blocking and D4 is 1:50~1:5.
Preferably, catalyst A and D4 mass ratio are 1 in step (1):100~1:20.
Preferably, in step (1), during the polysiloxane blocked using diamine base, catalyst A selects methyl hydrogen-oxygen
Change ammonium silicon alkoxide；During using double hydroxy-end capped polysiloxane, catalyst A selects tin acetate or Sn (Oct)2。
Preferably, the mass ratio of dimethyl silicone polymer and glycolide described in step (2) is 1:20~1:1.
Preferably, the catalyst B is one in tin catalyst, ferric acetyl acetonade, isocyanates, butyl titanate
Kind is several, and the addition of the catalyst B is glycolide mole 0.1%~1.0%.Tin catalyst is preferably tin acetate
Or Sn (Oct)2。
What a kind of a kind of preparation method based on organic-silicon-modified PGA as claimed in claim 1 was prepared has
Application of the machine Si modification PGA in 3D printing technique field.
Therefore, the present invention has the advantages that：(1) compared with traditional PGA, copolymer of the present invention
With the characteristic such as pliability is good, impact resistance is good, heat resistance is good；(2) compared with the physical modification of conventional PGA,
The present invention obtains PGA-polysiloxane block copolymer, copolymer materialization by this chemical method of modification by copolymerization
Performance is improved.
Embodiment
Technical scheme is further described with reference to embodiment.Reagent used below is
Purchased in market or normal experiment synthesizes to obtain.
Embodiment 1：
A kind of preparation method based on organic-silicon-modified PGA, step are as follows：By 1.0g 1,3- double (3- aminopropyls)-
1,1,3,3- tetramethyl disiloxane and 50g octamethylcy-clotetrasiloxanes (D4) are placed in four-neck flask, are heated up and are stirred under 600Pa
Mix, add 0.8g ammonium hydroxides ((CH3)4NOH) silicon alkoxide carries out ring-opening polymerization, is warming up to 140 DEG C, is removed under 50Pa
Low-boiling-point substance is gone to obtain the dimethyl silicone polymer of diamine base end-blocking.Add dichloromethane solvent stirring in a kettle afterwards,
80g glycolides are added afterwards, and add 1.0g catalyst acetic acid tin, after being passed through nitrogen exclusion air, are evacuated to 60Pa in 130 DEG C
16h is reacted, obtains PGA-polysiloxane block copolymers.
After tested, compared with PGA, the elongation at break of described PGA-polysiloxane block copolymers carries
High by 21%, heat decomposition temperature improves 16 DEG C.
Embodiment 2：
A kind of preparation method based on organic-silicon-modified PGA, step are as follows：By double (the 3- ethoxys) -1,1 of 20g 1,3-,
3,3- tetramethyl disiloxanes and 20g octamethylcy-clotetrasiloxanes (D4) are placed in four-neck flask, are heated up and are stirred under 1000Pa,
Add 0.2g tin acetates and carry out ring-opening polymerization, after be warming up to 160 DEG C, low-boiling-point substance is removed under 150Pa and obtains double hydroxyls envelopes
The dimethyl silicone polymer at end.80g glycolides are added after adding dichloromethane solvent stirring in a kettle afterwards, and are added
4.0g octoate catalyst stannous, after being passed through nitrogen exclusion air, it is evacuated to 200Pa and reacts 12h in 170 DEG C, obtain poly- second and hand over
Ester-polysiloxane block copolymers.
After tested, compared with PGA, the elongation at break of described PGA-polysiloxane block copolymers carries
High by 15%, heat decomposition temperature improves 14 DEG C.
Embodiment 3：
A kind of preparation method based on organic-silicon-modified PGA, step are as follows：By double (the 3- ethoxys) -1 of 0.1g 1,3-,
1,3,3- tetramethyl disiloxane and 10g octamethylcy-clotetrasiloxanes (D4) are placed in four-neck flask, are heated up and are stirred under 200Pa
Mix, add 0.5g tin acetates and carry out ring-opening polymerization, after be warming up to 250 DEG C, low-boiling-point substance is removed under 100Pa and obtains double hydroxyls
The dimethyl silicone polymer of end-blocking.80g glycolides are added after adding dichloromethane solvent stirring in a kettle afterwards, and are added
8.0g octoate catalyst stannous, after being passed through nitrogen exclusion air, it is evacuated to 120Pa and reacts 36h in 147 DEG C, obtain poly- second and hand over
Ester-polysiloxane block copolymers.
After tested, compared with PGA, the elongation at break of described PGA-polysiloxane block copolymers carries
High by 9%, heat decomposition temperature improves 9 DEG C.
Resulting copolymer, application practice can be carried out in 3D printing technique, good toughness is made, heat resistance is good
Complicated product, for fields such as bioengineering.
Above preferred embodiment is only intended to description and interpretation present disclosure, does not form the limit to present invention
System.Although inventor has done to the present invention and enumerated in more detail, those skilled in the art is according to the content of the invention
Content disclosed in part and embodiment, various modifications or/and supplement can be made to described specific embodiment or is adopted
To substitute it is obvious with similar mode, and the technique effect of the present invention can be realized, therefore, no longer repeats one by one herein.This
The term occurred in invention is used for elaboration and understanding to technical solution of the present invention, is not construed as limiting the invention.
Claims (10)
1. a kind of preparation method based on organic-silicon-modified PGA, it is characterised in that from the poly- silicon of difunctional end-blocking
Oxygen alkane oligomer mixes with glycolide in the presence of an organic, is copolymerized under catalyst B effects, and obtained PGA-
Polysiloxane block copolymers, i.e., described organic-silicon-modified PGA.
2. a kind of preparation method based on organic-silicon-modified PGA according to claim 1, it is characterised in that described
Preparation method be following steps：
（1）The agent of difunctional siloxane blocking and octamethylcy-clotetrasiloxane are mixed, heats up and stirs under 200~1000Pa,
Add catalyst A and carry out ring-opening polymerization, wait to be warming up to more than 140 DEG C, low-boiling-point substance is removed under 50~150Pa and obtains difunctionality
The dimethyl silicone polymer of group's end-blocking；
（2）In step（1）Described in dimethyl silicone polymer in be passed through nitrogen exclude air, add glycolide, organic molten
Added in the presence of agent and react 12 ~ 36h under catalyst B, 60~200Pa in 130~170 DEG C of oil baths, purified after being cooled to room temperature
Obtain the PGA-poly organo alkyl copolymer.
A kind of 3. preparation method based on organic-silicon-modified PGA according to claim 2, it is characterised in that step
（1）Described in difunctional siloxane blocking agent be 1,3- double (3- aminopropyls) -1,1,3,3- tetramethyl disiloxanes, 1,
Double (the 2- amino-ethyls) -1 of 3-, one or both of 1,3,3- tetramethyl disiloxane, or 1,3- bis (3-hydroxypropyl) -
One or both of double (2- ethoxys) -1,1,3,3- tetramethyl disiloxanes of 1,1,3,3- tetramethyl disiloxanes, 1,3-.
A kind of 4. preparation method based on organic-silicon-modified PGA according to claim 2, it is characterised in that step
（1）The mass ratio of middle difunctional siloxane blocking agent and octamethylcy-clotetrasiloxane is 1:100~1:1.
A kind of 5. preparation method based on organic-silicon-modified PGA according to claim 4, it is characterised in that step
（1）The mass ratio of middle difunctional siloxane blocking agent and octamethylcy-clotetrasiloxane is 1:50~1:5.
A kind of 6. preparation method based on organic-silicon-modified PGA according to claim 2, it is characterised in that step
（1）In, using diamine base block polysiloxane when, catalyst A selects ammonium hydroxide silicon alkoxide；Using double hydroxyls
During the polysiloxane of end-blocking, catalyst A selects tin acetate or Sn (Oct)2。
7. a kind of preparation method based on organic-silicon-modified PGA according to claim 2,3,4 or 6, its feature exist
In step（1）Middle catalyst A and octamethylcy-clotetrasiloxane mass ratio are 1:100~1:20.
A kind of 8. preparation method based on organic-silicon-modified PGA according to claim 2, it is characterised in that step
（2）Described in the mass ratio of dimethyl silicone polymer and glycolide be 1:20~1:1.
9. a kind of preparation method based on organic-silicon-modified PGA according to claim 2, it is characterised in that described
Catalyst B is tin catalyst, the one or more in ferric acetyl acetonade, isocyanates, butyl titanate, the catalyst B
Addition be glycolide mole 0.1% ~ 1.0%.
What 10. a kind of a kind of preparation method based on organic-silicon-modified PGA as claimed in claim 1 was prepared has
Application of the machine Si modification PGA in 3D printing technique field.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114479651A (en) * | 2021-11-08 | 2022-05-13 | 山东灵晓新材料有限公司 | Self-repairable UV (ultraviolet) photocureable coating and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103052672A (en) * | 2010-08-10 | 2013-04-17 | Lg化学株式会社 | Polysiloxane-polylactide block copolymer and preparation method thereof |
| CN106948178A (en) * | 2017-04-25 | 2017-07-14 | 苏州依司特新材料科技有限公司 | Organic silicon modified polyurethane anti-pilling finishing agent, preparation method and application |
| CN106977726A (en) * | 2017-04-18 | 2017-07-25 | 长春工业大学 | A kind of methylvinyl-polysiloxane biodegradable polyesters block copolymer |
-
2017
- 2017-10-27 CN CN201711031757.7A patent/CN107840949A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103052672A (en) * | 2010-08-10 | 2013-04-17 | Lg化学株式会社 | Polysiloxane-polylactide block copolymer and preparation method thereof |
| CN106977726A (en) * | 2017-04-18 | 2017-07-25 | 长春工业大学 | A kind of methylvinyl-polysiloxane biodegradable polyesters block copolymer |
| CN106948178A (en) * | 2017-04-25 | 2017-07-14 | 苏州依司特新材料科技有限公司 | Organic silicon modified polyurethane anti-pilling finishing agent, preparation method and application |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114479651A (en) * | 2021-11-08 | 2022-05-13 | 山东灵晓新材料有限公司 | Self-repairable UV (ultraviolet) photocureable coating and preparation method thereof |
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