CN110105747A - A kind of degradable water soluble elastomer and preparation method thereof - Google Patents
A kind of degradable water soluble elastomer and preparation method thereof Download PDFInfo
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- CN110105747A CN110105747A CN201910437234.5A CN201910437234A CN110105747A CN 110105747 A CN110105747 A CN 110105747A CN 201910437234 A CN201910437234 A CN 201910437234A CN 110105747 A CN110105747 A CN 110105747A
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
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- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
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- C08L2205/00—Polymer mixtures characterised by other features
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Abstract
The present invention provides a kind of degradable water soluble elastomer and preparation method thereof, and degradable water soluble elastomer includes using the copolymer of polylactic acid and polyethylene glycol as soft segment performed polymer, using the copolymer of sulfonic acid type hydrophilic monomer and isocyanates as the block copolymer of hard section performed polymer；Wherein the mass ratio of soft segment performed polymer and hard section performed polymer is (25-120): (25-80).Preparation method includes: that ring-opening polymerization is occurred in the presence of a catalyst for lactide and polyethylene glycol, obtains polylactic acid and ethylene glycol copolymer soft segment performed polymer；Polymerization reaction is occurred into for sulfonic acid type hydrophilic monomer and isocyanates, obtains sulfonic acid type hydrophilic monomer and isocyanate copolymer hard section performed polymer；Soft segment performed polymer is mixed with hard section performed polymer, polymerization reaction is carried out, obtains degradable water soluble elastomer.The degradable water soluble elastomer has good mechanical strength, has good dispersion performance in water, and degradable, has the feature of environmental protection.
Description
Technical field
The invention belongs to thermoplastic elastomer (TPE) technical fields, and in particular to a kind of degradable water soluble elastomer and its preparation
Method.
Background technique
Elastomer refers to that deformation is significant under weak stress, can be promptly restored to after stress relaxation close to original state and size
High molecular material.Elastomer includes rubber and thermoplastic elastomer (TPE), wherein thermoplastic elastomer (TPE) had both had the cross-linking vulcanized rubber of tradition
The high resiliency of glue, ageing-resistant, the every excellent properties of oil resistivity, while, processing method easy to process but also with common plastics is wide
Feature, and it is widely used in different field.
Thermoplastic polyurethane elastomer molecular structure is alternately arranged by soft segment and hard section and is formed, and has reduced TG transformation
The soft segment of temperature forms successional matrix, makes it have low temperature flexibility, and the hard section with high glass-transition temperature is by dividing
The interaction forces such as hydrogen bond physical crosslinking is formed between son and is self-assembly of hard section region, serves as the reinforcement in polyurethane elastomer
The filler of successive substrates.In certain special industrials and special oil gas engineering field, need to use some with water-soluble speciality
Elastomer as sealing material, and it is regulatable for needing its dispersion performance in water, meanwhile, to the mechanics of the elastomer
Intensity and heat resistance also there are certain requirements.
But the usual molecular weight of elastomer in the prior art is very big, the tangled structure of macromolecular chain complexity easy to form,
It can first be swollen after material water, then just can dissolve, it is water-soluble bad, it can not disperse well in water, it can not
Meet the needs of special industrial and special oil gas engineering field use.In addition, elastomer in the prior art can not drop mostly
Solution, especially in the water bodys such as ocean, river, elastomer class solid refuse generally requires century-old ability natural degradation and falls, largely
Using will cause serious environmental pollution；It requires to add poisonous and harmful class cooperation in many rubber and plastic class elastomer synthesis processes
Agent makes the elastomeric article as terminal often have certain toxicity.
Summary of the invention
The technical problem to be solved by the present invention is to provide a kind of degradable water soluble elastomers, have good mechanical strength,
There is good dispersion performance in water, and degradable, there is the feature of environmental protection.
To solve the above-mentioned problems, the present invention provides a kind of degradable water soluble elastomer comprising with polylactic acid and gathers
The copolymer of ethylene glycol is soft segment performed polymer, using the copolymer of sulfonic acid type hydrophilic monomer and isocyanates as the embedding of hard section performed polymer
Section copolymer.
Wherein, sulfonic acid type hydrophilic monomer refers to hydrophilic radicals such as hydroxyl, amino, and the monomer with sulfonate, for example,
1,4-butanediol -2- sodium sulfonate, N, N- bis- (2- ethoxy) -2-aminoethanesulfonic acid sodium etc., it is preferred that the choosing of sulfonic acid type hydrophilic monomer
Select 1,4- butanediol -2- sodium sulfonate.
Wherein, one or more of the optional diisocyanate of isocyanates, polyisocyanates.Preferably, isocyanates
For diisocyanate, it is further preferred that diisocyanate selects isophorone diisocyanate.
Wherein, polyethylene glycol preferred number average molecular weight is 1000-3000.
Degradable water soluble elastomer of the invention is using the copolymer of polylactic acid and polyethylene glycol as soft segment, with sulfonic acid type parent
The copolymer of aqueous monomer and isocyanates is hard section, and aggregated reaction generates the polyurethane knot of the block copolymer of soft segment and hard section
Structure, the elastomer in water when, be broken the macromolecular of block copolymer polyurethane structural after the ester linkage hydrolyzing in polylactic acid, shape
At the lesser molecular structure of molecular weight, since polylactic acid generates hydrophilic hydroxyl after ester linkage hydrolyzing, and the sulfonic acid in molecular structure
Type hydrophilic monomer is not only anionic group or strong hydrophilicity group, can make the lesser molecule knot of molecular weight generated after fracture
Structure has very strong water solubility, so that it is water-soluble well to have elastomer, the elastomer in water when and other elastomers
Then macromolecular chain is first swollen just dissolution difference, macromolecular chain is fractured into small molecule first, is then redispersed in water, will not
Swelling is first generated, and solubility property is more preferable；Further, it is also possible to pass through the polymerization of the ratio and polylactic acid of polylactic acid in regulatory molecule
The solubility property of degree regulation elastomer.In addition, the elastomer also has the good feature of environmental protection, poly- propionic acid is one in block copolymer
Kind generally acknowledge with good biodegradability properties can material, i.e. degradable and water soluble formation lactic acid after ester bond disconnects in molecule, so
It is afterwards that carbon dioxide and water can be degradable lactic acidosis by microorganism；Polyethylene glycol is water-soluble polymer, is ground
Study carefully and shows that the polyethylene glycol that molecular weight is more than 2000 is that the mankind can be by renal metabolism, for human body and with respect to peace
Complete；Though isocyanates class formation has certain toxicity, due to NCO group reactivity with higher, water or humidity are met
Air, which will react, generates nontoxic urea bond, and therefore, which has certain feature of environmental protection.
Wherein, it is preferred that in block copolymer, the mass ratio of soft segment performed polymer and hard section performed polymer is (25-120):
(25-80)。
Wherein, it is preferred that the mass ratio of polylactic acid component and polyethylene glycol is (5-20): (20- in soft segment performed polymer
100)。
Wherein, it is preferred that the mass ratio of sulfonic acid type hydrophilic monomer and isocyanates is (10-30) in hard section performed polymer:
(15-50)。
Wherein, it is preferred that the degradable water soluble elastomer further includes water-solubility function auxiliary agent, water-solubility function auxiliary agent with
The mass ratio of soft segment performed polymer is (5-50): (25-120).Water-solubility function auxiliary agent refers to the mechanical property that elastomeric material can be improved
The function additive of energy, and there is certain water soluble characteristic.Preferably, water-solubility function auxiliary agent is polyol, multiamide
One or more of compound.Polyol refers to that the compound in molecule containing great amount of hydroxy group, multiamide compound refer to
Contain the compound of a large amount of amide groups in molecule.Water-solubility function auxiliary agent selects polyol or multiamide compound,
Hydroxyl, amide group in water-solubility function auxiliary agent can be with the ammonia ester bonds in the polyurethane structural of the block copolymer in elastomer
Hydrogen bond is formed, makes the two because Hydrogenbond attracts each other, guarantees the excellent mechanical performances of elastomeric material, and when water is present,
Hydrogen bond action between hydrogen bond, hydrone between hydrone and polyurethane and polyhydroxy, multiamide water-solubility function auxiliary agent is greater than two
Hydrogen bond action between person keeps polyurethane structural and water-solubility function auxiliary agent soluble in water, to not influence the water of elastomer
Dissolubility.In addition, generating a large amount of ducts in the elastomer, more just after the water-solubility function auxiliary agent in elastomer is dissolved in the water
Enter inside elastomer in hydrone, promotes the hydrolysis of polylactic acid ester bond in block copolymer macromolecular, promote the degradation of material
And dissolution.It is further preferred that water-solubility function auxiliary agent is one of polyacrylamide, polyvinyl alcohol, guar gum or several
Kind.
Wherein, it is preferred that the degradable water soluble elastomer further includes dispersing agent, the quality of dispersing agent and soft segment performed polymer
Than for (5-50): (25-120), after the block copolymer degradation of the polyurethane structural of elastomer, dispersing agent can enhancing degradation obtain
The dispersion degree of each small molecule compound arrived in water.Wherein, dispersing agent is preferably Sodium Polyacrylate.
It is a further object of the present invention to provide a kind of methods for preparing above-mentioned degradable water soluble elastomer, including following step
It is rapid:
S1. ring-opening polymerization is occurred into for the lactide of calculation amount and polyethylene glycol in the presence of a catalyst, obtains poly- cream
Acid and ethylene glycol copolymer soft segment performed polymer；
S2. polymerization reaction is occurred into for the sulfonic acid type hydrophilic monomer of calculation amount and isocyanates, obtains sulfonic acid type hydrophilic monomer
With isocyanate copolymer hard section performed polymer；
S3. the soft segment performed polymer in step S1 is mixed with the hard section performed polymer in step S2, carries out polymerization reaction, obtains
Degradable water soluble elastomer.
Wherein, the mass ratio of catalyst and lactide is (0.01-0.5): (5-20), the optional isooctyl acid bismuth of catalyst, the moon
One or more of cinnamic acid bismuth, two carboxyethyl germanium sesquioxide germanium.
Preferably, step S1 specifically: mix the lactide, polyethylene glycol, catalyst of calculation amount, in protective atmosphere
It is reacted 2-10 hours at 180-200 DEG C, then the reaction was continued under the pressure of -0.095~-0.098Mpa 0.5-2h is obtained
The copolymer of polylactic acid and polyethylene glycol.Wherein, protective atmosphere refers to that the inert gas that will not be reacted with raw material, protective atmosphere are optional
Nitrogen, helium, argon gas etc., it is preferred that protective atmosphere is nitrogen.
Preferably, step S2 specifically: mix the sulfonic acid type hydrophilic monomer of calculation amount with isocyanates, in protective atmosphere
In reacted 2-4 hours at 60-80 DEG C, obtain the copolymer of sulfonic acid type hydrophilic monomer and isocyanates.Wherein, protective atmosphere refers to
The inert gas that will not be reacted with raw material, the optional nitrogen of protective atmosphere, helium, argon gas etc., it is preferred that protective atmosphere is nitrogen.
Preferably, step S3 specifically: by the soft segment performed polymer that step S1 is obtained and the hard section performed polymer that step S2 is obtained
Mixing, reacts at 170-200 DEG C, obtains degradable water soluble elastomer.It is further preferred that step S3 specifically: will walk
The soft segment performed polymer that rapid S1 is obtained is mixed with the hard section performed polymer that step S2 is obtained, then use response type double screw extruder in
Extruding pelletization at 170-200 DEG C obtains degradable water soluble elastomer.
Wherein, it is preferred that when mixing soft segment performed polymer with hard section performed polymer in step S3, be additionally added water-solubility function and help
Agent and dispersing agent.Preferably, water-solubility function auxiliary agent is one or more of polyol, multiamide compound；Into
One step is preferred, and water-solubility function auxiliary agent is one or more of polyacrylamide, polyvinyl alcohol, guar gum；Preferably,
Dispersing agent is Sodium Polyacrylate.
Wherein, it is preferred that when mixing soft segment performed polymer with hard section performed polymer in step S3, it is additionally added inner pattern releasing agent applicable, it is interior
The mass ratio of release agent and soft segment performed polymer is (1-5): (25-120).Knockout course when inner pattern releasing agent applicable can be such that material injection completes
It is easier to the problem of carrying out, sticking to mould does not occur, is conducive to the injection molding of elastomer.Wherein, inner pattern releasing agent applicable can for hydroxy silicon oil,
One or both of amido silicon oil.
Compared with the prior art, the present invention has the following beneficial effects:
1. degradable water soluble elastomer of the invention has high tensile strength, high elongation at tear and high hardness,
Therefore there is good mechanical strength；
2. degradable water soluble elastomer of the invention has good dispersion performance in water, and water soluble characteristic is controllable.It should
Degradable water soluble elastomer is using the copolymer of polylactic acid and polyethylene glycol as soft segment, with sulfonic acid type hydrophilic monomer and isocyanates
Copolymer be hard section, aggregated reaction generates the polyurethane structural of the block copolymer of soft segment and hard section, and the elastomer is in water
It when middle, is broken the macromolecular of block copolymer polyurethane structural after the ester linkage hydrolyzing in polylactic acid, it is lesser to form molecular weight
Molecular structure, the sulfonic acid type hydrophilic monomer since polylactic acid generates hydrophilic hydroxyl after ester linkage hydrolyzing, and in molecular structure, not only
It is anionic group or strong hydrophilicity group, can makes the lesser molecular structure of molecular weight generated after fracture that there is very strong water
Dissolubility can also pass through the ratio of polylactic acid in regulatory molecule and polylactic acid so that it is water-soluble well to have elastomer
The solubility property of degree of polymerization regulation elastomer；
3. the water-solubility function auxiliary agent in elastomer can be with the block in elastomer containing great amount of hydroxy group or amide group
Ammonia ester bond in the polyurethane structural of copolymer forms hydrogen bond, makes the two because Hydrogenbond attracts each other, and guarantees elastomeric material
Excellent mechanical performances, and when water is present, the hydrogen bond, hydrone and polyhydroxy, multiamide between hydrone and polyurethane are water-soluble
Hydrogen bond action between sexual function auxiliary agent is greater than hydrogen bond action between the two, keeps polyurethane structural and water-solubility function auxiliary agent molten
Yu Shuizhong, so that the water solubility of elastomer is not influenced, in addition, after the water-solubility function auxiliary agent in elastomer is dissolved in the water,
A large amount of ducts are generated in the elastomer, and hydrone of being more convenient for enters inside elastomer, promotes to gather cream in block copolymer macromolecular
The hydrolysis of acid esters key promotes the degradation and dissolution of material, at the same time it can also pass through the water-solubility function in regulation elastomeric material
The solubility property of the amount regulation elastomer of auxiliary agent；
4. degradable water soluble elastomer of the invention has the good feature of environmental protection, polylactic acid is a kind of in elastomer structure
It is generally acknowledged with good biodegradability properties can material, i.e. degradable and water soluble formation lactic acid after ester bond disconnects in molecule, then
It can be degradable for carbon dioxide and water lactic acidosis by microorganism；Polyethylene glycol is water-soluble polymer, molecular weight
Polyethylene glycol more than 2000 is that the mankind can be also comparatively safe for human body by renal metabolism；Isocyanic acid
Though esters structure has certain toxicity, due to NCO group reactivity with higher, meeting water or humid air will react
Generate nontoxic urea bond；
5. degradable water soluble elastomer processing performance of the invention is good, there is good thermoplasticity.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical solution of the present invention is clearly and completely described, it is clear that
Described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based on the implementation in the present invention
Example, every other embodiment obtained by those of ordinary skill in the art without making creative efforts belong to
The scope of protection of the invention.
Embodiment 1
Degradable water soluble elastomer described in the present embodiment, the component including following mass fraction:
Using the copolymer of polylactic acid and polyethylene glycol as soft segment performed polymer, with 1,4- butanediol -2- sodium sulfonate and different Fo Er
The copolymer of ketone diisocyanate is 185 parts of block copolymer of hard section performed polymer；30 parts of polyacrylamide；Polyvinyl alcohol 20
Part；5 parts of hydroxy silicon oil；5 parts of Sodium Polyacrylate.
Wherein, the mass ratio of polylactic acid and polyethylene glycol is 5:100 in soft segment performed polymer；The number-average molecular weight of polyethylene glycol
It is 1000；
1,4- butanediol -2- sodium sulfonate and the mass ratio of isophorone diisocyanate are 30:50 in hard section performed polymer.
The preparation method of degradable water soluble elastomer described in the present embodiment is specific as follows:
S1. 100 parts of cetomacrogol 1000s, 5 parts of lactides and 0.5 part of catalyst isooctyl acid bismuth are put into reaction kettle,
Under nitrogen protection environment, it is stirred to react in 180~200 DEG C 2 hours, -0.098Mpa then is evacuated down to reaction kettle, continue to stir
Reaction 1h is mixed, that is, the copolymer polyols of polylactic acid and polyethylene glycol are prepared, is soft segment performed polymer；
S2. 30 parts of 1,4-butanediol -2- sodium sulfonates are put into reaction kettle together with 50 parts of isophorone diisocyanate,
Under nitrogen protection environment, it is stirred to react in 60 DEG C 4 hours, that is, 1,4-butanediol -2- sodium sulfonate and isophorone is prepared
The copolymer of diisocyanate is hard section performed polymer；
S3. the soft segment performed polymer in step S1, the hard section performed polymer in step S2,30 parts of polyacrylamides, 20 parts are gathered
Vinyl alcohol, 5 parts of hydroxy silicon oils, 5 parts of Sodium Polyacrylates are put into storage tank together after being stirred, and are squeezed by response type twin-screw
170~200 DEG C of extruding pelletizations of machine out obtain the degradable water soluble elastomer of the present embodiment.
Embodiment 2
Degradable water soluble elastomer described in the present embodiment, the component including following mass fraction:
Using the copolymer of polylactic acid and polyethylene glycol as soft segment performed polymer, with 1,4- butanediol -2- sodium sulfonate and different Fo Er
The copolymer of ketone diisocyanate is 100 parts of block copolymer of hard section performed polymer；50 parts of guar gum；5 parts of amido silicon oil；It is poly-
50 parts of sodium acrylate.
Wherein, the mass ratio of polylactic acid and polyethylene glycol is 1:1 in soft segment performed polymer；The number-average molecular weight of polyethylene glycol is
2000；
1,4- butanediol -2- sodium sulfonate and the mass ratio of isophorone diisocyanate are 1:1 in hard section performed polymer.
The preparation method of degradable water soluble elastomer described in the present embodiment is specific as follows:
S1. 20 parts of polyethylene glycol 2000s, 20 parts of lactides and 0.01 part of catalyst lauric acid bismuth are put into reaction kettle,
Under nitrogen protection environment, it is stirred to react in 180~200 DEG C 5 hours, -0.095Mpa then is evacuated down to reaction kettle, continue to stir
Reaction 1h is mixed, that is, the copolymer polyols of polylactic acid and polyethylene glycol are prepared, is soft segment performed polymer；
S2. 30 parts of 1,4-butanediol -2- sodium sulfonates are put into reaction kettle together with 30 parts of isophorone diisocyanate,
Under nitrogen protection environment, it is stirred to react in 80 DEG C 2 hours, that is, 1,4-butanediol -2- sodium sulfonate and isophorone is prepared
The copolymer of diisocyanate is hard section performed polymer；
S3. by the soft segment performed polymer in step S1, the hard section performed polymer in step S2,50 parts of guar gums, 5 parts of amino silicones
Oil, 50 parts of Sodium Polyacrylates are put into storage tank together after being stirred, and pass through 170~200 DEG C of response type double screw extruder
Extruding pelletization obtains the degradable water soluble elastomer of the present embodiment.
Embodiment 3
Degradable water soluble elastomer described in the present embodiment, the component including following mass fraction:
Using the copolymer of polylactic acid and polyethylene glycol as soft segment performed polymer, with 1,4- butanediol -2- sodium sulfonate and different Fo Er
The copolymer of ketone diisocyanate is 185 parts of block copolymer of hard section performed polymer；3 parts of polyacrylamide, 2 parts of polyvinyl alcohol,
5 parts of hydroxy silicon oil, 5 parts of Sodium Polyacrylate.
Wherein, the mass ratio of polylactic acid and polyethylene glycol is 1:20 in soft segment performed polymer；The number-average molecular weight of polyethylene glycol
It is 1000；
1,4- butanediol -2- sodium sulfonate and the mass ratio of isophorone diisocyanate are 3:5 in hard section performed polymer.
The preparation method of degradable water soluble elastomer described in the present embodiment is specific as follows:
S1. 100 parts of cetomacrogol 1000s, 5 parts of lactides and 0.5 part of catalyst lauric acid bismuth are put into reaction kettle,
Under nitrogen protection environment, it is stirred to react in 180~200 DEG C 5 hours, -0.098Mpa then is evacuated down to reaction kettle, continue to stir
Reaction 1h is mixed, that is, the copolymer polyols of polylactic acid and polyethylene glycol are prepared, is soft segment performed polymer；
S2. 30 parts of 1,4-butanediol -2- sodium sulfonates are put into reaction kettle together with 50 parts of isophorone diisocyanate,
Under nitrogen protection environment, it is stirred to react in 60 DEG C 4 hours, that is, 1,4-butanediol -2- sodium sulfonate and isophorone is prepared
The copolymer of diisocyanate is hard section performed polymer；
S3. by the soft segment performed polymer in step S1, the hard section performed polymer in step S2,3 parts of polyacrylamides, 2 parts of poly- second
Enol, 5 parts of hydroxy silicon oils, 5 parts of Sodium Polyacrylates are put into storage tank together after being stirred, and response type twin-screw extrusion is passed through
170~200 DEG C of extruding pelletizations of machine, obtain the degradable water soluble elastomer of the present embodiment.
Embodiment 4
Degradable water soluble elastomer described in the present embodiment, the component including following mass fraction:
Using the copolymer of polylactic acid and polyethylene glycol as soft segment performed polymer, with 1,4- butanediol -2- sodium sulfonate and different Fo Er
The copolymer of ketone diisocyanate is 135 parts of block copolymer of hard section performed polymer；50 parts of guar gum, gathers 1 part of amido silicon oil
30 parts of sodium acrylate.
Wherein, the mass ratio of polylactic acid and polyethylene glycol is 1:10 in soft segment performed polymer；The number-average molecular weight of polyethylene glycol
It is 3000；
1,4- butanediol -2- sodium sulfonate and the mass ratio of isophorone diisocyanate are 10:15 in hard section performed polymer.
The preparation method of degradable water soluble elastomer described in the present embodiment is specific as follows:
S1. 100 parts of Macrogol 3000s, 10 parts of lactides and 0.3 part of catalyst lauric acid bismuth are put into reaction kettle,
It under nitrogen protection environment, is stirred to react in 180~200 DEG C 10 hours, -0.095Mpa then is evacuated down to reaction kettle, continued
It is stirred to react 1h, that is, the copolymer polyols of polylactic acid and polyethylene glycol are prepared, is soft segment performed polymer；
S2. 10 parts of 1,4-butanediol -2- sodium sulfonates are put into reaction kettle together with 15 parts of isophorone diisocyanate,
Under nitrogen protection environment, it is stirred to react in 80 DEG C 2 hours, that is, 1,4-butanediol -2- sodium sulfonate and isophorone is prepared
The copolymer of diisocyanate is hard section performed polymer；
S3. by the soft segment performed polymer in step S1, the hard section performed polymer in step S2,50 parts of guar gums, 1 part of amino silicone
Oil, 30 parts of Sodium Polyacrylates are put into storage tank together after being stirred, and pass through 170~200 DEG C of response type double screw extruder
Extruding pelletization obtains the degradable water soluble elastomer of the present embodiment.
Embodiment 5
Degradable water soluble elastomer described in the present embodiment, the component including following mass fraction:
Using the copolymer of polylactic acid and polyethylene glycol as soft segment performed polymer, with 1,4- butanediol -2- sodium sulfonate and different Fo Er
The copolymer of ketone diisocyanate is 135 parts of block copolymer of hard section performed polymer；10 parts of guar gum, gathers 5 parts of amido silicon oil
30 parts of sodium acrylate.
Wherein, the mass ratio of polylactic acid and polyethylene glycol is 1:10 in soft segment performed polymer；The number-average molecular weight of polyethylene glycol
It is 3000；
1,4- butanediol -2- sodium sulfonate and the mass ratio of isophorone diisocyanate are 10:15 in hard section performed polymer.
The preparation method of degradable water soluble elastomer described in the present embodiment is specific as follows:
S1. by 100 parts of Macrogol 3000s, 10 parts of lactides, 0.2 part of catalyst isooctyl acid bismuth, 0.1 part of catalyst laurel
In sour bismuth investment reaction kettle, under nitrogen protection environment, it is stirred to react 2 hours, then reaction kettle is taken out true in 180~200 DEG C
Sky arrives -0.095Mpa, continues to be stirred to react 1h, that is, the copolymer polyols of polylactic acid and polyethylene glycol are prepared, and is soft segment
Performed polymer；
S2. 10 parts of 1,4-butanediol -2- sodium sulfonates are put into reaction kettle together with 15 parts of isophorone diisocyanate,
Under nitrogen protection environment, it is stirred to react in 80 DEG C 2 hours, that is, 1,4-butanediol -2- sodium sulfonate and isophorone is prepared
The copolymer of diisocyanate is hard section performed polymer；
S3. by the soft segment performed polymer in step S1, the hard section performed polymer in step S2,10 parts of guar gums, 5 parts of amino silicones
Oil, 30 parts of Sodium Polyacrylates are put into storage tank together after being stirred, and pass through 170~200 DEG C of response type double screw extruder
Extruding pelletization obtains the degradable water soluble elastomer of the present embodiment.
Embodiment 6
Degradable water soluble elastomer described in the present embodiment, the component including following mass fraction:
Using the copolymer of polylactic acid and polyethylene glycol as soft segment performed polymer, with 1,4- butanediol -2- sodium sulfonate and different Fo Er
The copolymer of ketone diisocyanate is 135 parts of block copolymer of hard section performed polymer；10 parts of guar gum；5 parts of amido silicon oil；It is poly-
30 parts of sodium acrylate.
Wherein, the mass ratio of polylactic acid and polyethylene glycol is 1:10 in soft segment performed polymer；The number-average molecular weight of polyethylene glycol
It is 3000；
1,4- butanediol -2- sodium sulfonate and the mass ratio of isophorone diisocyanate are 10:15 in hard section performed polymer.
The preparation method of degradable water soluble elastomer described in the present embodiment is specific as follows:
S1. 100 parts of Macrogol 3000s, 10 parts of lactides, 0.3 part of two carboxyethyl germanium sesquioxide germanium of catalyst investment is anti-
It answers in kettle, under nitrogen protection environment, is stirred to react 2 hours in 180~200 DEG C, then reaction kettle is evacuated down to-
0.095Mpa continues to be stirred to react 1h, that is, the copolymer polyols of polylactic acid and polyethylene glycol is prepared, and is soft segment pre-polymerization
Body；
S2. 10 parts of 1,4-butanediol -2- sodium sulfonates are put into reaction kettle together with 15 parts of isophorone diisocyanate,
Under nitrogen protection environment, it is stirred to react in 80 DEG C 2 hours, that is, 1,4-butanediol -2- sodium sulfonate and isophorone is prepared
The copolymer of diisocyanate is hard section performed polymer；
S3. by the soft segment performed polymer in step S1, the hard section performed polymer in step S2,10 parts of guar gums, 5 parts of amino silicones
Oil, 30 parts of Sodium Polyacrylates are put into storage tank together after being stirred, and pass through 170~200 DEG C of response type double screw extruder
Extruding pelletization obtains the degradable water soluble elastomer of the present embodiment.
Embodiment 7
Degradable water soluble elastomer described in the present embodiment, the component including following mass fraction:
Using the copolymer of polylactic acid and polyethylene glycol as soft segment performed polymer, with 1,4- butanediol -2- sodium sulfonate and different Fo Er
The copolymer of ketone diisocyanate is 135 parts of block copolymer of hard section performed polymer；50 parts of guar gum；5 parts of amido silicon oil；It is poly-
30 parts of sodium acrylate.
Wherein, the mass ratio of polylactic acid and polyethylene glycol is 1:10 in soft segment performed polymer；The number-average molecular weight of polyethylene glycol
It is 3000；
1,4- butanediol -2- sodium sulfonate and the mass ratio of isophorone diisocyanate are 10:15 in hard section performed polymer.
The preparation method of degradable water soluble elastomer described in the present embodiment is specific as follows:
S1. 100 parts of Macrogol 3000s, 10 parts of lactides, 0.3 part of two carboxyethyl germanium sesquioxide germanium of catalyst investment is anti-
It answers in kettle, under nitrogen protection environment, is stirred to react 2 hours in 180~200 DEG C, then reaction kettle is evacuated down to-
0.095Mpa continues to be stirred to react 1h, that is, the copolymer polyols of polylactic acid and polyethylene glycol is prepared, and is soft segment pre-polymerization
Body；
S2. 10 parts of 1,4-butanediol -2- sodium sulfonates are put into reaction kettle together with 15 parts of isophorone diisocyanate,
Under nitrogen protection environment, it is stirred to react in 80 DEG C 2 hours, that is, 1,4-butanediol -2- sodium sulfonate and isophorone is prepared
The copolymer of diisocyanate is hard section performed polymer；
S3. by the soft segment performed polymer in step S1, the hard section performed polymer in step S2,50 parts of guar gums, 5 parts of amino silicones
Oil, 30 parts of Sodium Polyacrylates are put into storage tank together after being stirred, and pass through 170~200 DEG C of response type double screw extruder
Extruding pelletization obtains the degradable water soluble elastomer of the present embodiment.
Embodiment 8
Degradable water soluble elastomer described in the present embodiment, the component including following mass fraction:
Using the copolymer of polylactic acid and polyethylene glycol as soft segment performed polymer, with 1,4- butanediol -2- sodium sulfonate and different Fo Er
The copolymer of ketone diisocyanate is 165 parts of block copolymer of hard section performed polymer；30 parts of polyacrylamide；Polyvinyl alcohol 20
Part；5 parts of hydroxy silicon oil；5 parts of Sodium Polyacrylate.
Wherein, the mass ratio of polylactic acid and polyethylene glycol is 5:100 in soft segment performed polymer；The number-average molecular weight of polyethylene glycol
It is 1000；
1,4- butanediol -2- sodium sulfonate and the mass ratio of isophorone diisocyanate are 10:50 in hard section performed polymer.
The preparation method of degradable water soluble elastomer described in the present embodiment is in the same manner as in Example 1, and difference exists
What is be added in S2 is 10 parts of 1,4- butanediol -2- sodium sulfonates and 50 parts of isophorone diisocyanate.
Embodiment 9
Degradable water soluble elastomer described in the present embodiment, the component including following mass fraction:
Using the copolymer of polylactic acid and polyethylene glycol as soft segment performed polymer, with 1,4- butanediol -2- sodium sulfonate and different Fo Er
The copolymer of ketone diisocyanate is 150 parts of block copolymer of hard section performed polymer；30 parts of polyacrylamide；Polyvinyl alcohol 20
Part；5 parts of hydroxy silicon oil；5 parts of Sodium Polyacrylate.
Wherein, the mass ratio of polylactic acid and polyethylene glycol is 5:100 in soft segment performed polymer；The number-average molecular weight of polyethylene glycol
It is 1000；
1,4- butanediol -2- sodium sulfonate and the mass ratio of isophorone diisocyanate are 30:15 in hard section performed polymer.
The preparation method of degradable water soluble elastomer described in the present embodiment is in the same manner as in Example 1, and difference exists
What is be added in S2 is 30 parts of 1,4- butanediol -2- sodium sulfonates and 15 parts of isophorone diisocyanate.
Embodiment 10
Degradable water soluble elastomer described in the present embodiment, the component including following mass fraction:
Using the copolymer of polylactic acid and polyethylene glycol as soft segment performed polymer, with 1,4- butanediol -2- sodium sulfonate and different Fo Er
The copolymer of ketone diisocyanate is 105 parts of block copolymer of hard section performed polymer；30 parts of polyacrylamide；Polyvinyl alcohol 20
Part；5 parts of hydroxy silicon oil；5 parts of Sodium Polyacrylate.
Wherein, the mass ratio of soft segment performed polymer and hard section performed polymer is 25:80；
The mass ratio of polylactic acid and polyethylene glycol is 5:20 in soft segment performed polymer；The number-average molecular weight of polyethylene glycol is
1000；
1,4- butanediol -2- sodium sulfonate and the mass ratio of isophorone diisocyanate are 30:50 in hard section performed polymer.
The preparation method of degradable water soluble elastomer described in the present embodiment is in the same manner as in Example 1.
Embodiment 11
Degradable water soluble elastomer described in the present embodiment, the component including following mass fraction:
Using the copolymer of polylactic acid and polyethylene glycol as soft segment performed polymer, with 1,4- butanediol -2- sodium sulfonate and different Fo Er
The copolymer of ketone diisocyanate is 145 parts of block copolymer of hard section performed polymer；30 parts of polyacrylamide；Polyvinyl alcohol 20
Part；5 parts of hydroxy silicon oil；5 parts of Sodium Polyacrylate.
Wherein, the mass ratio of soft segment performed polymer and hard section performed polymer is 120:25；
The mass ratio of polylactic acid and polyethylene glycol is 20:100 in soft segment performed polymer；The number-average molecular weight of polyethylene glycol is
1000；
1,4- butanediol -2- sodium sulfonate and the mass ratio of isophorone diisocyanate are 10:15 in hard section performed polymer.
The preparation method of degradable water soluble elastomer described in the present embodiment is in the same manner as in Example 1.
Embodiment 12
Degradable water soluble elastomer described in the present embodiment, other compositions, preparation method are same as Example 1, different
Place is N, N- bis- (2- ethoxy) -2-aminoethanesulfonic acid sodium in sulfonic acid type hydrophilic monomer in this present embodiment.
Embodiment 13
Degradable water soluble elastomer described in the present embodiment, other compositions, preparation method are same as Example 1, different
Place is toluene di-isocyanate(TDI) in isocyanates in this present embodiment.
Comparative example 1
Elastomer described in the comparative example, the component including following mass fraction:
Using the homopolymer of Macrogol 3000 as soft segment performed polymer, with 1,4-butanediol -2- sodium sulfonate and isophorone two
The copolymer of isocyanates is 125 parts of block copolymer of hard section performed polymer；10 parts of guar gum, 5 parts of amido silicon oil, polypropylene
30 parts of sour sodium.
Wherein, 1,4-butanediol -2- sodium sulfonate and the mass ratio of isophorone diisocyanate are 10 in hard section performed polymer:
15。
The method for producing elastomers of the comparative example is specific as follows:
S1. 100 parts of Macrogol 3000s and 0.2 part of catalyst isooctyl acid bismuth, 0.1 part of catalyst lauric acid bismuth investment are anti-
It answers in kettle, under nitrogen protection environment, 180~200 DEG C are stirred to react 2 hours, then reaction kettle is evacuated down to-
0.095Mpa continues to be stirred to react 1h, that is, polyethylene glycol polyalcohol is prepared.
S2. 10 parts of 1,4-butanediol -2- sodium sulfonates and 15 parts of isophorone diisocyanate are put into reaction kettle together,
Under nitrogen protection environment, 80 DEG C are stirred to react 2 hours, that is, are prepared as hard section performed polymer.
S3. polyethylene glycol polyalcohol, the obtained hard section performed polymer of step S2 and measure 10 for taking step S1 to obtain
Part guar gum, 5 parts of amido silicon oils, 30 parts of Sodium Polyacrylates are put into storage tank together after being stirred, and it is double to pass through response type
170~200 DEG C of extruding pelletizations of screw extruder, obtain elastomer.
Comparative example 2
Elastomer described in the comparative example, the component including following mass fraction:
Using the copolymer of polylactic acid and Macrogol 3000 as soft segment performed polymer, with 1,4- butanediol -2- sodium sulfonate with it is different
The copolymer of isophorone diisocyanate is 135 parts of block copolymer of hard section performed polymer；10 parts of guar gum；Amido silicon oil 5
Part.
Wherein, the mass ratio of polylactic acid and polyethylene glycol is 1:10 in soft segment performed polymer；The number-average molecular weight of polyethylene glycol
It is 3000.
Wherein, 1,4-butanediol -2- sodium sulfonate and the mass ratio of isophorone diisocyanate are 10 in hard section performed polymer:
15。
The method for producing elastomers of the comparative example is specific as follows:
S1. by 100 parts of Macrogol 3000s, 10 parts of lactides and 0.2 part of catalyst isooctyl acid bismuth, 0.1 part of catalyst moon
Cinnamic acid bismuth is put into reaction kettle, and under nitrogen protection environment, 180~200 DEG C are stirred to react 2 hours, is then taken out to reaction kettle true
Sky arrives -0.095Mpa, continues to be stirred to react 1h, that is, the copolymer polyols of polylactic acid and polyethylene glycol are prepared, and is soft segment
Performed polymer.
S2. 10 parts of 1,4-butanediol -2- sodium sulfonates and 15 parts of isophorone diisocyanate are put into reaction kettle together,
Under nitrogen protection environment, 80 DEG C are stirred to react 2 hours, that is, are prepared as hard section performed polymer.
S3. soft segment performed polymer, the obtained hard section performed polymer of step S2 and the 10 portions of melons measured for taking step S1 to obtain
That bean gum, 5 parts of amido silicon oils are put into storage tank together after being stirred, and pass through 170~200 DEG C of response type double screw extruder
Extruding pelletization obtains elastomer.
Comparative example 3
Elastomer described in the comparative example, the component including following mass fraction:
Using the copolymer of polylactic acid and polyethylene glycol 400 as soft segment performed polymer, with 1,4- butanediol -2- sodium sulfonate and different Buddhist
The copolymer of your ketone diisocyanate is 185 parts of block copolymer of hard section performed polymer；3 parts of polyacrylamide；Polyvinyl alcohol 2
Part；5 parts of hydroxy silicon oil；5 parts of Sodium Polyacrylate.
Wherein, the mass ratio of polylactic acid and polyethylene glycol is 1:20 in soft segment performed polymer；The number-average molecular weight of polyethylene glycol
It is 400.
Wherein, 1,4-butanediol -2- sodium sulfonate and the mass ratio of isophorone diisocyanate are 3 in hard section performed polymer:
5。
The method for producing elastomers of the comparative example is specific as follows:
S1. 100 parts of polyethylene glycol 400s, 5 parts of lactides and 0.5 part of catalyst lauric acid bismuth are put into reaction kettle, in nitrogen
Under gas shielded environment, 180~200 DEG C are stirred to react 5 hours, are then evacuated down to -0.098Mpa to reaction kettle, and it is anti-to continue stirring
1h is answered, that is, the copolymer polyols of polylactic acid and polyethylene glycol are prepared, is soft segment performed polymer.
S2. 30 parts of 1,4-butanediol -2- sodium sulfonates and 50 parts of isophorone diisocyanate are put into reaction kettle together,
Under nitrogen protection environment, 60 DEG C are stirred to react 4 hours, that is, are prepared as hard section performed polymer.
S3. the soft segment performed polymer that takes step S1 to obtain, the obtained hard section performed polymer of step S2 and measure 3 parts poly- third
Acrylamide, 2 parts of polyvinyl alcohol, 5 parts of hydroxy silicon oils, 5 parts of Sodium Polyacrylates are put into storage tank together after being stirred, by anti-
170~200 DEG C of extruding pelletizations of type double screw extruder are answered, elastomer is obtained.
Comparative example 4
Elastomer described in the comparative example, the component including following mass fraction:
Using the copolymer of polylactic acid and cetomacrogol 1000 as soft segment performed polymer, with 1,4- butanediol -2- sodium sulfonate with it is different
The copolymer of isophorone diisocyanate is 185 parts of block copolymer of hard section performed polymer；3 parts of polyacrylamide；Polyvinyl alcohol 2
Part；5 parts of hydroxy silicon oil.
Wherein, the mass ratio of polylactic acid and polyethylene glycol is 1:20 in soft segment performed polymer；The number-average molecular weight of polyethylene glycol
It is 1000.
Wherein, 1,4-butanediol -2- sodium sulfonate and the mass ratio of isophorone diisocyanate are 3 in hard section performed polymer:
5。
The method for producing elastomers of the comparative example is specific as follows:
S1. 100 parts of cetomacrogol 1000s, 5 parts of lactides and 0.5 part of catalyst lauric acid bismuth are put into reaction kettle,
Under nitrogen protection environment, 180~200 DEG C are stirred to react 5 hours, are then evacuated down to -0.098Mpa to reaction kettle, are continued to stir
1h is reacted, that is, the copolymer polyols of polylactic acid and polyethylene glycol are prepared, is soft segment performed polymer.
S2. 30 parts of 1,4-butanediol -2- sodium sulfonates and 50 parts of isophorone diisocyanate are put into reaction kettle together,
Under nitrogen protection environment, 60 DEG C are stirred to react 4 hours, that is, are prepared as hard section performed polymer.
S3. the soft segment performed polymer that takes step S1 to obtain, the obtained hard section performed polymer of step S2 and measure 3 parts poly- third
Acrylamide, 2 parts of polyvinyl alcohol, 5 parts of hydroxy silicon oils are put into storage tank together after being stirred, and response type twin-screw extrusion is passed through
170~200 DEG C of extruding pelletizations of machine, obtain elastomer.
Comparative example 5
Elastomer described in the comparative example, the component including following mass fraction:
Using the copolymer of polylactic acid and Macrogol 3000 as soft segment performed polymer, with 1,4- butanediol -2- sodium sulfonate with it is different
The copolymer of isophorone diisocyanate is 135 parts of block copolymer of hard section performed polymer；10 parts of guar gum；Sodium Polyacrylate
30 parts.
Wherein, the mass ratio of polylactic acid and polyethylene glycol is 1:10 in soft segment performed polymer；The number-average molecular weight of polyethylene glycol
It is 3000.
Wherein, 1,4-butanediol -2- sodium sulfonate and the mass ratio of isophorone diisocyanate are 10 in hard section performed polymer:
15。
The method for producing elastomers of the comparative example is specific as follows:
S1. by 100 parts of Macrogol 3000s, 10 parts of lactides and 0.2 part of catalyst isooctyl acid bismuth, 0.1 part of catalyst moon
Cinnamic acid bismuth is put into reaction kettle, and under nitrogen protection environment, 180~200 DEG C are stirred to react 2 hours, is then taken out to reaction kettle true
Sky arrives -0.095Mpa, continues to be stirred to react 1h, that is, the copolymer polyols of polylactic acid and polyethylene glycol are prepared, and is soft segment
Performed polymer.
S2. 10 parts of 1,4-butanediol -2- sodium sulfonates and 15 parts of isophorone diisocyanate are put into reaction kettle together,
Under nitrogen protection environment, 80 DEG C are stirred to react 2 hours, that is, are prepared as hard section performed polymer.
S3. soft segment performed polymer, the obtained hard section performed polymer of step S2 and the 10 portions of melons measured for taking step S1 to obtain
Your bean gum, 30 parts of Sodium Polyacrylates are put into storage tank together after being stirred, by response type double screw extruder 170~
200 DEG C of extruding pelletizations, obtain elastomer.
Comparative example 6
Elastomer described in the comparative example, the component including following mass fraction:
Using the copolymer of polylactic acid and Macrogol 3000 as soft segment performed polymer, with 1,4- butanediol -2- sodium sulfonate with it is different
The copolymer of isophorone diisocyanate is 135 parts of block copolymer of hard section performed polymer；10 parts of guar gum；Amido silicon oil 5
Part；30 parts of Sodium Polyacrylate.
Wherein, the mass ratio of polylactic acid and polyethylene glycol is 1:10 in soft segment performed polymer；The number-average molecular weight of polyethylene glycol
It is 3000.
Wherein, 1,4-butanediol -2- sodium sulfonate and the mass ratio of isophorone diisocyanate are 10 in hard section performed polymer:
15。
The method for producing elastomers of the comparative example is specific as follows:
S1. 100 parts of Macrogol 3000s, 10 parts of lactides are put into reaction kettles, under nitrogen protection environment, 180~
200 DEG C are stirred to react 2 hours, are then evacuated down to -0.095Mpa to reaction kettle, continue to be stirred to react 1h, that is, are prepared poly-
The copolymer polyols of lactic acid and polyethylene glycol are soft segment performed polymer.
S2. 10 parts of 1,4-butanediol -2- sodium sulfonates and 15 parts of isophorone diisocyanate are put into reaction kettle together,
Under nitrogen protection environment, 80 DEG C are stirred to react 2 hours, that is, are prepared as hard section performed polymer.
S3. soft segment performed polymer, the obtained hard section performed polymer of step S2 and the 10 portions of melons measured for taking step S1 to obtain
That bean gum, 5 parts of amido silicon oils, 30 parts of Sodium Polyacrylates are put into storage tank together after being stirred, and response type twin-screw is passed through
170~200 DEG C of extruding pelletizations of extruder, obtain elastomer.
The mechanical property, injection molding performance, solubility property of the elastomer of above-described embodiment and comparative example are tested.
The preparations of test bars and injection molding Performance Evaluation: 170~200 DEG C of injection temperature, coinjection stretch performance, hardness and molten
Batten needed for solving performance test, the injection molding machine used is Jiaxing Ke Su Machinery Co., Ltd., KS-8502R type injection molding machine.
GB/T528-1998 standard is pressed in the tensile property test of elastomer, in RG1-5 type electronic universal tester (Shenzhen
Rui Geer Instrument Ltd. production) on carry out tensile property test；The hardness performance of elastomer is according to GB/T531 standard in Shao
Hardness test is carried out on family name's A type hardness tester meter (Yangzhou De Rui Instrument Ltd.).
Solubility property test: it will be molded after the weighing of obtained GB/T528-1998 standard dumbbell batten that (dumbbell batten is molten
Weight remembers m before solution is tested1) put into 100ml beaker, add water 800ml, entire flask is put into the hot bath of different temperatures
After dissolving 120h, the material in flask is all crossed into 20 mesh screens, scraping is not dried in 130 DEG C of baking ovens by the component of sieve
5h, (its quality is denoted as m for weighing2).The dissolution rate of elastomer is (m1-m2)/m1。
The mechanical property of the elastomer of each embodiment, comparative example, injection molding performance, solubility property test result is as follows table 1.
Table 1
The degradable water soluble elastomer of the application has high tensile strength, height it can be seen from above-mentioned experimental data
Elongation at break and high hardness, therefore mechanical strength is high；And the degradable water soluble elastomer of the application is water-soluble very well；
In addition, the degradable water soluble elastomer of the application also has good processing performance, there is good thermoplasticity.
The elastomer phase ratio of elastomer in comparative example 1 and the embodiment of the present application 5 does not contain polylactic acid monomer in soft segment,
Its dispersion performance in water is very poor, and serious swelling occurs in water.
The elastomer phase ratio and comparative example 4 and the embodiment of the present application 3 of elastomer and the embodiment of the present application 5 in comparative example 2
Elastomer phase ratio, dispersing agent is not added in elastic production procedure, the dispersion performance of elastomer in water is very poor, sends out in water
Raw serious swelling.
The elastomer phase ratio of elastomer in comparative example 3 and the embodiment of the present application 3, the polyalkylene glycol monomer in soft segment is number
The polyethylene glycol that average molecular weight is 400, elongation at break is minimum, and texture is different from elastomer, therefore, with the poly- of low molecular weight
Ethylene glycol is that elastomer can not be prepared in the monomer in soft segment.
Interior demoulding is not added in preparation process for the elastomer phase ratio of elastomer in comparative example 5 and the embodiment of the present application 5
Agent, product sticking to mould is serious after injection moulding process, can not remove from mold, injection molding rate is very poor.
The elastomer phase ratio in elastomer and the embodiment of the present application 5 in comparative example 6, soft segment preparation are not used urge in the process
Agent, particle stretch intensity obtained is extremely low, elongation at break is extremely low, hardness very little, and mechanical strength is too poor, leads to not make
Grain.
Obviously, the above embodiments are merely examples for clarifying the description, and does not limit the embodiments.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of variation or
It changes.There is no necessity and possibility to exhaust all the enbodiments.And it is extended from this it is obvious variation or
It changes still within the protection scope of the invention.
Claims (10)
1. a kind of degradable water soluble elastomer, it is characterised in that: it is soft that it, which includes with the copolymer of polylactic acid and polyethylene glycol,
Section performed polymer, using the copolymer of sulfonic acid type hydrophilic monomer and isocyanates as the block copolymer of hard section performed polymer.
2. degradable water soluble elastomer according to claim 1, it is characterised in that: the soft segment performed polymer and described hard
The mass ratio of section performed polymer is (25-120): (25-80).
3. degradable water soluble elastomer according to claim 1, it is characterised in that: polylactic acid in the soft segment performed polymer
The mass ratio of component and polyethylene glycol is (5-20): (20-100).
4. degradable water soluble elastomer according to claim 1, it is characterised in that: sulfonic acid type in the hard section performed polymer
The mass ratio of hydrophilic monomer and isocyanates is (10-30): (15-50).
5. degradable water soluble elastomer according to claim 1, it is characterised in that: it further include water-solubility function auxiliary agent,
The mass ratio of the water-solubility function auxiliary agent and the soft segment performed polymer is (5-50): (25-120), the water-solubility function help
Agent is one or more of polyol, multiamide compound.
6. degradable water soluble elastomer according to claim 1, it is characterised in that: it further include dispersing agent, the dispersion
The mass ratio of agent and the soft segment performed polymer is (5-50): (25-120), and the dispersing agent is Sodium Polyacrylate.
7. degradable water soluble elastomer according to claim 1, it is characterised in that: the equal molecule of the number of the polyethylene glycol
Amount is 1000-3000.
8. a kind of method for preparing degradable water soluble elastomer as claimed in claim 1, which is characterized in that including
Following steps:
S1. ring-opening polymerization is occurred into for the lactide of calculation amount and polyethylene glycol in the presence of a catalyst, obtains the poly- cream
The soft segment performed polymer of acid and the copolymer of polyethylene glycol；
S2. polymerization reaction is occurred into for the sulfonic acid type hydrophilic monomer of calculation amount and isocyanates, obtains the sulfonic acid type hydrophilic monomer
With the hard section performed polymer of the copolymer of isocyanates；
S3. the soft segment performed polymer in step S1 is mixed with the hard section performed polymer in step S2, carries out polymerization reaction,
Obtain the degradable water soluble elastomer.
9. the method according to claim 8 for preparing degradable water soluble elastomer, it is characterised in that: by institute in step S3
When stating soft segment performed polymer and mixing with the hard section performed polymer, it is additionally added water-solubility function auxiliary agent and dispersing agent.
10. the method according to claim 8 for preparing degradable water soluble elastomer, it is characterised in that: will in step S3
When the soft segment performed polymer is mixed with the hard section performed polymer, it is additionally added inner pattern releasing agent applicable, the inner pattern releasing agent applicable and the soft segment are pre-
The mass ratio of aggressiveness is (1-5): (25-120).
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| CN114247888A (en) * | 2021-12-08 | 2022-03-29 | 蓝山县金山川粉末冶金有限公司 | Method for manufacturing transmission gear through powder metallurgy |
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