阅读说明：本技术 弹性体、其制备方法及其用途 (Elastomer, Its Preparation Method And Use ) 是由 陈景 那海宁 朱锦 吕素平 陈祥纪 于 2017-03-02 设计创作，主要内容包括：公开了分段式热塑性弹性体,其可以是聚氨酯、聚脲或聚氨酯-脲,其包含软段和硬段,其中,软段由聚烯烃二醇或聚烯烃二胺制成,所述聚烯烃二醇或聚烯烃二胺的主链中可以具有0至1000个碳原子,其中,主链中的每个碳原子可以具有0至2个侧链,并且每个侧链可以具有0至30个碳原子,硬段由二异氰酸酯和增链剂制成,硬段占弹性体的10-60％,而软段占剩余部分,弹性体的数均分子量是5×10<Sup>3</Sup>-1000×10<Sup>3</Sup>克/摩尔；弹性体的极限伸长率是100-1000％；杨氏模量是1-3,000MPa；并且极限拉伸强度是10-100MPa。还公开了用于制备所述分段式热塑性弹性体的方法及所述分段式热塑性弹性体的用途。(Disclose segmented thermoplastic elastomer (TPE), it can be polyurethane, polyureas or polyurethane-urea, it includes soft segments and hard section, wherein, soft segment is made of polyolefin diols or polyolefin diamines, it can have 0 to 1000 carbon atom in the main chain of the polyolefin diols or polyolefin diamines, wherein, each carbon atom in main chain can have 0 to 2 side chain, and each side chain can have 0 to 30 carbon atom, hard section is made of diisocyanate and cahin extension agent, hard section accounts for the 10-60% of elastomer, and soft segment accounts for remainder, the number-average molecular weight of elastomer is 5 × 10 3 ‑1000×10 3 Gram/mol；The ultimate elongation of elastomer is 100-1000%；Young's modulus is 1-3,000MPa；And ultimate tensile strength is 10-100MPa.Also disclose the purposes of the method for being used to prepare the segmented thermoplastic elastomer (TPE) and the segmented thermoplastic elastomer (TPE).)

1. a kind of segmented thermoplastic elastomer (TPE), can be polyurethane, polyureas or polyurethane-urea, by soft segment and hard section group At, wherein

Soft segment is made of polyolefin diols or polyolefin diamines, can have in the main chain of the polyolefin diols or polyolefin diamines There is 0 to 1000 carbon atom, wherein each carbon atom in main chain can have 0 to 2 side chain, and each side chain can be with With 0 to 30 carbon atom,

Hard section is made of diisocyanate and cahin extension agent,

Hard section accounts for the 10-60% of elastomer, and soft segment accounts for remainder,

The number-average molecular weight of elastomer is 5 × 10³-1000×10³Gram/mol；The ultimate elongation of elastomer is 100- 1000%；Young's modulus is 1-3,000MPa；And ultimate tensile strength is 10-100MPa.

2. elastomer according to claim 1, which is characterized in that number-average molecular weight is 10 × 10³-300×10³Gram/rub You；Ultimate elongation is 200-700%；Young's modulus is 10-2,000MPa；And ultimate tensile strength is 10-100MPa.

3. elastomer according to claim 1, wherein soft segment is formed by following substance: polybutadiene diol, poly- isoamyl two Enediol, polybutene glycol, macrogol, polypropylene glycol, poly- (ethylene-propylene) copolymer diol, polyisobutene glycol, Branched polyethylene glycol, polybutene diamines, polyethylenediamine, polypropylenediamine, poly- (ethylene-propylene) copolymer diamines, gather it is different Butylene diamines, branched polyethylene diamines and its mixture.

4. elastomer according to claim 1, wherein diisocyanate is selected from Toluene-2,4-diisocyanate, 4- diisocyanate, its isomery Or mixtures thereof body；4,4 '-'-diphenylmethane diisocyanates, hexamethylene diisocyanate, isophorone diisocyanate, 4, 4 '-two (cyclohexyl) methane diisocyanates, di-2-ethylhexylphosphine oxide (cyclohexyl) diisocyanate, trans- 1,4- hexamethylene diisocyanate Ester, paraphenylene diisocyanate, lysine diisocyanate, terephthalylidene diisocyanate, 1,5- pentamethylene diisocyanate Ester, to tetramethylxylene diisocyanate, tetramethylxylene diisocyanate and its mixture.

5. elastomer according to claim 1, wherein cahin extension agent be selected from ethylene glycol, 1,3-PD, 1,4-butanediol, 1,4- hexylene glycol, 1,4- cyclohexanediol, 1,6-HD, 1,8- ethohexadiol, 1,9- nonanediol, 1,10- decanediol, ethylenediamine, Propane diamine, butanediamine, hexamethylene diamine, cyclohexanediamine and its mixture.

6. elastomer as claimed in claim 3, which is characterized in that soft segment is hydrogenated polybutadiene diol.

7. elastomer according to claim 3, which is characterized in that soft segment is hydrogenated polyisoprene glycol.

8. a kind of method for preparing elastomer, the described method comprises the following steps:

(i) preparation has the glycol of unsaturated bond, hydrogenates the glycol then to obtain hydrogenated diol, wherein in the main chain of glycol With 1 to 1000 carbon atom, wherein each carbon atom in main chain has 0 to 2 side chain, and each side chain have 0 to 30 carbon atoms, the side chain are alkyl or cycloalkyls；

(ii) microwave radiation is used, using diisocyanate and polymerization catalyst, the hydrogenated diol obtained in step (i) is carried out Prepolymerization is to obtain polyurethane prepolymer；And

(iii) cahin extension agent is added in polyurethane prepolymer, and is persistently polymerize using microwave radiation to obtain poly- ammonia Ester.

9. according to the method described in claim 8, it is characterized in that, in step (i), by two pure and mild noble metal hydrogenation catalysts It is added in hydrogenation reactor so that diol hydrogenation.

10. according to the method described in claim 9, reaction pressure is 0.1- it is characterized in that, reaction temperature is 0-200 DEG C 100MPa, and the reaction time is 1-24h；And the noble metal hydrogenation catalyst is one of Pt race metal.

11. according to the method described in claim 8, diisocyanate is selected from Toluene-2,4-diisocyanate it is characterized in that, in step (ii), Or mixtures thereof 4- diisocyanate, its isomers；It is 4,4 '-'-diphenylmethane diisocyanates, hexamethylene diisocyanate, different It is isophorone diisocyanate, 4,4 '-two (cyclohexyl) methane diisocyanates, di-2-ethylhexylphosphine oxide (cyclohexyl) diisocyanate, trans- 1,4- cyclohexane diisocyanate, paraphenylene diisocyanate, lysine diisocyanate, terephthalylidene diisocyanate, 1,5- pentamethylene diisocyanate, to tetramethylxylene diisocyanate, tetramethylxylene diisocyanate and its mixed Close object；

Polymerization catalyst is selected from: triethylenediamine, dibutyl tin dilaurate, stannous octoate and its mixture；And

Prepolymerization temperature is 50-200 DEG C, and prepolymerization time is 1-5h；Microwave irradiation power is adjusted so that reaction temperature is maintained at In expected range.

12. according to the method for claim 11, which is characterized in that prepolymerization temperature is 65 DEG C to 95 DEG C.

13. according to the method described in claim 8, it is characterized in that, cahin extension agent is selected from ethylene glycol, 1,3- in step (iii) Propylene glycol, 1,4- butanediol, 1,4- hexylene glycol, 1,4- cyclohexanediol, 1,6-HD, 1,8- ethohexadiol, 1,9- nonanediol, 1, 10- decanediol, ethylenediamine, propane diamine, butanediamine, hexamethylene diamine, cyclohexanediamine and its mixture；And

Polymerization temperature is 50-250 DEG C, and polymerization time is 1-5h；And adjust microwave irradiation power so that reaction mixture temperature Degree is positively retained in expected range.

14. according to the method for claim 12, which is characterized in that prepolymerization temperature is 65 DEG C to 95 DEG C.

15. according to the method described in claim 8, it is characterized in that, step (i)-(iii) in the presence of a solvent, In, the solvent is selected from toluene, dimethylbenzene, tetrahydrofuran, chloroform, n,N-Dimethylformamide, ethyl acetate, N, N- dimethyl Acetamide, dimethyl sulfoxide and its mixture.

16. a kind of method for preparing elastomer, the described method comprises the following steps:

(i) preparation has the glycol and/or diamines of unsaturated bond, hydrogenates the glycol and/or diamines then to obtain hydrogenated diol And/or diamines, wherein there is 1 to 1000 carbon atom, wherein every in main chain in the main chain of glycol and/or diamines A carbon atom has 0 to 2 side chain, and each side chain has 0 to 30 carbon atom, wherein the side chain is alkyl or ring Alkyl；

(ii) microwave radiation is used, using diisocyanate and polymerization catalyst, to the hydrogenated diol obtained in step (i), two Or mixtures thereof amine carries out prepolymerization to obtain prepolymer；And

(iii) cahin extension agent is added in prepolymer, and is persistently polymerize using microwave radiation to obtain elastomer.

17. a kind of method for preparing elastomer, the described method comprises the following steps:

(i) preparation has the glycol or diamines of unsaturated bond；

(ii) microwave radiation is used, using diisocyanate and polymerization catalyst, acquisition glycol in step (i) or diamines are carried out Prepolymerization is to obtain polyurethane or polyurea prepolymer；And

(iii) cahin extension agent is added in polyurethane or polyurea prepolymer, and is persistently polymerize using microwave radiation to obtain Obtain polyurethane or polyureas；And

(iv) polyurethane or polyureas are hydrogenated in the presence of a catalyst.

18. polyurethane described in any one of -7 is in medical device, coating, fiber, adhesive or foam material according to claim 1 Purposes in material.

19. a kind of medical device comprising elastomer as described in claim 1.

Technical field

The invention belongs to macromolecular material field, it is related to the polyurethane comprising polyolefin soft segment.More specifically, the present invention relates to And polyurethane, Its Preparation Method And Use.

Background technique

Polyolefin is a kind of polymeric material, and chain has soft segment and hard section.Due to this special structure, polyurethane material It is high with many excellent properties, such as low-temperature resistance, wear-resistant, in biotic environment stability, therefore it is widely used in boat Empty product, medical device, coating, textiles and leathers.Currently, the polyurethane material for medical device is often with there is following knot Structure: soft segment and hard section, the soft segment are formed by oligomeric polyols, and the oligomeric polyols such as polytetrahydrofuran (PTMO) gathers Dimethyl siloxane (PDMS) or aliphatic polycarbonate, and the hard section is by diisocyanate that [such as 4,4 '-diphenyl-methanes two are different Cyanate (MDI) or hydrogenation MDI (HMDI)] and cahin extension agent [such as 1,4- butanediol (BDO)] formation.However, making in long-term With period, polyether-type or polycarbonate polyurethane can be by oxidation, hydrolysis or enzymatic reaction chemical degradations, this can lead to material Material failure, or even make failure of apparatus under certain conditions.For example, when polyether polyurethane material is used for long-term implant When, it is oxidable.The oxidation as caused by inflammatory reaction often occurs at the apparatus surface contacted with tissue.This is referred to as environment and answers Power cracking.The oxidation reaction occurred at the apparatus surface contacted with certain metal surfaces (such as cobalt and its alloy) is referred to as The oxidation of metal ion induction.

In general, the oxidizable degradation of ehter bond.Unfortunately, there are oxidisability chemical substances in the organism of patient. Therefore, solve the problems, such as that this key is to develop the polyurethane material as composed by Antioxidation reaction soft segment more stronger than polyethers Material.A variety of polyurethane with novel soft segment, such as polycarbonate polyurethane [Lubrizol Corp. are had been developed in the past (Lubrizol) Carbothane^TM, DSM N. V. Bionate^TMDeng), PDMS polyurethane (Biomerics company ElastEon^TM, DSM N. V. Pursil^TMDeng) etc..These new materials have been proven that with improved oxidative degradation. However, they have the problem of hydrolytic degradation.

Recently, the polyurethane material made of polyisobutene soft segment shows excellent anti-oxidant and hydrolytic degradation.So And it synthesizes this material and needs complicated process.Producing commercial-scale material with comparable cost is still a problem.In Past suggest using macrogol [bibliography 1:M.D.Benz, K.Bonnema, E.Didomenico, C.Hobot, D.Miller, " Medical devices constaining segmented polyurethane biomaterials " (contain Have the medical device of segmented polyurethane biomaterial), US 6,915,168].Assuming that the polyurethane meeting made of polyethylene sections With good anti-oxidant and hydrolysis.Seemingly with polyisobutene polyurethanes, the synthesis technology of polyvinyl polyurethane there are still Technological challenge, this continues the commercialization for having postponed material.

Therefore, it is still necessary to which exploitation manufactures the effective ways of polyurethane material for producing polyolefin diols.

Summary of the invention

The present invention is a kind of method for effectively preparing Polyolefin based polyurethane.The method consists of two parts.First Divide is to manufacture polyolefin diols by polymerize then hydrogenation to diene.Second part is made by using microwave heating Make polyurethane material.The Polyolefin based polyurethane manufactured in this way is estimated to have excellent property for chronobiological medicine Implantation application.

Technical solution

The purpose of the present invention can be realized by the following contents:

{ 1 } polyurethane, polyureas or polyurethane-urea elastomers composition can be defined as the reaction product of following substance:

1) macromolecular diol or macromolecular diamine, including hydrogenated polyolefins glycol, hydrogenated polyolefins diamines or hydrogenation are poly- Olefin diols, hydrogenated polyolefins diamines, polyetherdiol and/or polycarbonate glycol mixture, wherein polyolefin diols are poly- It can have 0 to 1000 carbon atom in the main chain of olefinic diamines, wherein each carbon atom in main chain can have 0 to 2 Side chain, and each side chain can have 0 to 30 carbon atom,

2) diisocyanate, and

3) cahin extension agent；

{ 2 } polyurethane according to { 1 }, polyureas or polyurethane-urea elastomers composition, which is characterized in that the elasticity The number-average molecular weight of composition is 5 × 10³-1000×10³Gram/mol；The ultimate elongation of the elastic composition is 100- 1000%；Flexural modulus is 1-3,000MPa；And the ultimate tensile strength of the elastic composition is 10-100MPa.

{ 3 } polyurethane according to { 1 }, polyureas or polyurethane-urea elastomers composition, which is characterized in that described big point Sub- glycol be preferably chosen from polybutadiene diol, polyisoprene glycol, polybutene glycol, macrogol, polypropylene glycol, Poly- (ethylene-propylene) copolymer diol, polyisobutene glycol and its mixture；

The diisocyanate is selected from Toluene-2,4-diisocyanate, or mixtures thereof 4- diisocyanate (TDI), its isomers；4,4 '-two Phenylmethane diisocyanate (MDI), hexamethylene diisocyanate, isophorone diisocyanate, di-2-ethylhexylphosphine oxide (cyclohexyl) Diisocyanate (HMDI), trans- 1,4- cyclohexane diisocyanate (CHDI), paraphenylene diisocyanate, lysine diisocyanate Ester, terephthalylidene diisocyanate, 1,5- pentamethylene diisocyanate, to tetramethylxylene diisocyanate, four Methylxylene diisocyanate and its mixture；Wherein, particularly preferred MDI；And

Cahin extension agent be selected from ethylene glycol, 1,3- propylene glycol, 1,4- butanediol, 1,4- hexylene glycol, 1,4- cyclohexanediol, 1,6- oneself Glycol, 1,8- ethohexadiol, 1,9- nonanediol (nondadiol), 1,10- decanediol, ethylenediamine, propane diamine, butanediamine, oneself two Amine, cyclohexanediamine and its mixture；Wherein, particularly preferred 1,4-butanediol.

{ 4 } polyurethane according to { 3 }, polyureas or polyurethane-urea elastomers composition, which is characterized in that described big point Sub- glycol is hydrogenated polybutadiene diol or hydrogenated polyisoprene glycol.

{ 5 } a kind of method for being used to prepare polyurethane, polyureas or polyurethane-urea elastomers composition comprising following steps:

(i) preparation has the glycol of unsaturated bond, is then hydrogenated glycol to obtain hydrogenated diol, wherein described Glycol has a structure that

Wherein, n is the integer of 1-1000；And R¹And R²It independently is H, C_1-30Alkyl, C_3-30Naphthenic base or C_2-30Alkenyl；

(ii) microwave radiation is used, using diisocyanate and polymerization catalyst, to the hydrogenated diol obtained in step (i) Prepolymerization is carried out to obtain polyurethane prepolymer；And

(iii) cahin extension agent is added in polyurethane prepolymer, and is persistently polymerize using microwave radiation to obtain Polyurethane.

{ 6 } method according to { 5 }, which is characterized in that in step (i), by two pure and mild noble metal hydrogenation catalysts It is added in hydrogenation reactor so that diol hydrogenation.

{ 7 } method according to { 6 }, which is characterized in that reaction temperature is 0-200 DEG C, and reaction pressure is 0.1- 100MPa, and the reaction time is 1-24h；And the noble metal hydrogenation catalyst is one of Pt race metal.

{ 8 } method according to { 5 }, which is characterized in that in step (ii), diisocyanate is selected from Toluene-2,4-diisocyanate, 4- Or mixtures thereof diisocyanate (TDI), its isomers；4,4 '-'-diphenylmethane diisocyanates (MDI), hexa-methylene two are different Cyanate, isophorone diisocyanate, di-2-ethylhexylphosphine oxide (cyclohexyl) diisocyanate (HMDI), trans- 1,4- hexamethylene two are different Cyanate (CHDI), paraphenylene diisocyanate, lysine diisocyanate, terephthalylidene diisocyanate, 1,5- ring penta Alkane diisocyanate, to tetramethylxylene diisocyanate, tetramethylxylene diisocyanate and its mixture；

Polymerization catalyst is selected from: triethylenediamine, dibutyl tin dilaurate, stannous octoate and its mixture；And

Prepolymerization temperature is 50-200 DEG C, and prepolymerization time is 1-5h；Microwave irradiation power is adjusted to keep the temperature at In expected range, for example, the reaction-ure mixture to 50mL to 800mL applies 300-600W.

{ 9 } method according to { 8 }, which is characterized in that prepolymerization temperature is 65 DEG C to 95 DEG C.

{ 10 } method according to { 5 }, which is characterized in that in step (iii), cahin extension agent is selected from ethylene glycol, 1,3- Propylene glycol, 1,4- butanediol, 1,4- hexylene glycol, 1,4- cyclohexanediol, 1,6-HD, 1,8- ethohexadiol, 1,9- nonanediol, 1, 10- decanediol, to hydrobenzoin, rosin dimethanol (colophony dimethol), ethylenediamine, propane diamine, butanediamine, Hexamethylene diamine, cyclohexanediamine and its mixture；And

Polymerization temperature is 50-250 DEG C, and polymerization time is 2-3h；Adjust microwave irradiation power so that reaction mixture temperature Degree is maintained in expected range, for example, the reaction-ure mixture to 50mL to 800mL applies 300-600W.

{ 11 } method according to { 10 }, which is characterized in that prepolymerization temperature is 65 DEG C to 95 DEG C.

{ 12 } method according to { 5 }, which is characterized in that step (i)-(iii) in the presence of a solvent, In, the solvent is selected from toluene, dimethylbenzene, tetrahydrofuran, chloroform, n,N-Dimethylformamide, ethyl acetate, N, N- dimethyl Acetamide, dimethyl sulfoxide and its mixture.

{ 13 } a kind of alternative for being used to prepare identical polyurethane, polyureas or polyurethane-urea elastomers composition, packet It includes following steps: (1) preparing unsaturated diol by being polymerize to diene, (2) prepare polyurethane and (3) for polymer hydrogen It is melted into saturated polyurethane.

{ 14 } polyurethane according to any one of { 1 }-{ 4 } is in medical device, coating, fiber, adhesive or foam Purposes in material.

Beneficial effect

The present invention provides a kind of production methods, provide for preparation saturation macrogol and other polyolefin diols Feasible approach.This method is simple and efficient.It particularly, can be with lower instrument cost, shorter compared to conventional method Reaction time, higher yield, less by-product and lower energy consumption realize the method.It is suitable for extensive continuous raw It produces.

It can be used for medical device, coating, fiber, adhesive or foamed material with the product that the method manufactures.

Detailed description of the invention

Fig. 1 shows the UV absorption spectrum of the polytetramethylene glycol before the hydrogenation in embodiment 1 and after hydrogenation.

Fig. 2 shows the IR spectrum of the polyurethane obtained in embodiment 1.

Specific embodiment

The definition of term

Term in the application is defined as follows:

Polymerization is the chemical reaction between many monomers of one or more types.The reaction is so that form long-chain point Son.The reactive group of monomer is connected chemically together and becomes different groups.For example, the hydroxyl of a monomer and another monomer Isocyanates can react and form carbamate groups.Carbamate groups are present in polymer chain and play bonding Effect.

Glycol is tool there are two the organic compound of hydroxyl, and the hydroxyl can be anti-with the isocyanate groups of other compounds It answers.

Diisocyanate is tool there are two the organic compound of isocyanate groups, and the isocyanate groups can be with hydroxyl Reaction forms carbamate groups.

Cahin extension agent is that molecular weight is less than 200D and has that there are two the compounds of hydroxyl that can be reacted with isocyanates.Chain Agent is also possible to the compound that diamines or one end have hydroxyl with the amine other end, such as 4- amino-n-butyl alcohol.

Catalyst is the compound that can accelerate to react but be not a part of reaction product.

Unsaturated soft segment glycol is the soft segment glycol comprising C=C double bond or other unsaturated hydrocarbons keys.

Hydrogenation is unsaturated alkyl to be converted into the reaction of saturated group by addition hydrogen atom, such as C=C is converted into C-C.The reaction usually requires hydrogen and catalyst.

Polyurethane prepolymer is the polymer with following property: molecular weight is 50D to 10,000D and in each molecule End tool there are two isocyanate groups, which can react to form carbamate groups with cahin extension agent.

Polyurethane is to be formed by polymer by reacting between glycol and diisocyanate cpd.It is formed by ammonia Carbamate group is the key compound between monomer.

Branch is the chemical group that backbone structure is chemically attached to as side group.Polymer chain can have 1 or more than 1 Branch.Branch can be identical or different.Some examples of branch are methyl, ethyl, propyl, butyl, isobutyl group etc..

Microwave radiation reactor is a kind of chemical reactor, can be reacted under microwave radiation in the reactor.It is logical Normal microwave radiation reactor has non-contact infrared temperature sensor, can be used for monitoring the temperature and root of reaction mixture Temperature is controlled according to real-time condition.

In one embodiment, above-mentioned polyurethane can be manufactured in the following manner with two steps.

In the first step, the glycol having following structure is manufactured:

Wherein, n is the integer of 1-1000；R¹And R²It independently is H, C_1-30Alkyl, C_3-30Naphthenic base or C_2-30Alkenyl.

In order to obtain the structure in the first step, diene monomers appropriate or diene monomers group appropriate are selected.Diene monomers It is polymerized alone or is copolymerized with other alkene monomers, for both of these case, use hydrogen peroxide as catalyst.Diene includes but not It is limited to butadiene, isoprene etc..Alkene monomer includes but is not limited to ethylene, propylene, butylene, isobutene and combinations thereof.Pass through tune The ratio of whole total double bond and hydrogen peroxide can control the molecular weight of polydiene.Anionic polymerisation, living radical can also be passed through Polymerization and/or other polymerization reactions simultaneously then terminate two end of the chains formation diol structures with hydroxyl to manufacture polydiene.

In second step, structure (I) obtained in the first step is hydrogenated to following saturated diols (II):

Wherein, n is the integer of 1-1000；R³And R⁴It independently is H, C_1-30Alkyl or C_3-30Naphthenic base.

The glycol of structure (II) is hydrogenated polyvinyl glycol, hydrogenation polypropylene glycol, hydrogenated polybutene glycol, the poly- fourth of hydrogenation Cyclohexadienediol, hydrogenation polypenthylene glycol, poly- (4-methyl-1-pentene) glycol of hydrogenation, hydrogenation polyhexene glycol, the poly- (ethylene-of hydrogenation Propylene) copolymer diol or Parleam glycol.

During preparing polyurethane, water removal and/or other impurities is gone to be hydrogenated again, first to avoid in hydrogenation catalyst Poison.Those skilled in the art will be appreciated that deimpurity method.A kind of method can be apply while heating mixture it is true Sky carries out the duration appropriate.

In in the first aspect, the present invention provides the polyurethane made of soft segment glycol or diamines, polyureas or polyurethane- Urea elastomers, the soft segment glycol or diamines include but is not limited to hydrogenated polyolefins glycol, hydrogenated polyolefins diamines or hydrogenation Polyolefin diols, hydrogenated polyolefins diamines, polyetherdiol and/or polycarbonate glycol mixture.Polyolefin diols or polyene It can have 0 to 1000 carbon atom in the main chain of hydrocarbon diamines, wherein each carbon atom in main chain can have 0 to 2 side Chain, and each side chain can have 0 to 30 carbon atom.

In the present invention, the number-average molecular weight of elastomer is 5 × 10³-1,000×10³Gram/mol, preferably 100 × 10³- 600×10³Gram/mol；The ultimate elongation of elastomer is 100-1000%；Young's modulus is 1-3,000MPa；And elasticity The ultimate tensile strength of body is 10-100MPa.

In second aspect, the present invention provides the methods for preparing above-mentioned polyurethane, the described method comprises the following steps:

(i) glycol is hydrogenated to obtain hydrogenated diol；

(ii) microwave radiation is used, using diisocyanate and polymerization catalyst, to the hydrogenated diol obtained in step (i) Prepolymerization is carried out to obtain polyurethane prepolymer；And

(iii) cahin extension agent is added in polyurethane prepolymer, and is persistently polymerize using microwave radiation to obtain Polyurethane.

In the present invention, in step (i), two alcohol and solvents are added in reactor (such as hydrogenation reactor)；To After glycol dissolution, noble metal hydrogenation catalyst and hydrogen are added in reactor；Temperature and pressure is controlled in expected range It is interior and make reaction be continued until reaction complete；And separation, purifying and dry hydrogenated diol.

In the present invention, in step (i), the volume of hydrogenation reactor is 1-3L, and reaction temperature is 0-200 DEG C, preferably 50-150 DEG C, reaction pressure is 0.1-100MPa, and the reaction time is 1-24h；And the noble metal hydrogenation catalyst is Pt race One of metal (that is, Ru, Rh, Pd, Os, Ir and Pt) carried catalyst.

In the present invention, in step (ii), before carrying out prepolymerization, in a vacuum to the hydrogen obtained in step (i) Change soft segment to be heated and be dehydrated, wherein the temperature of heating and dehydration is 80-120 DEG C, and the time heated and be dehydrated is 1- 6h。

In the present invention, in step (ii), diisocyanate is selected from Toluene-2,4-diisocyanate, 4- diisocyanate (TDI), its isomery Or mixtures thereof body；4,4 '-'-diphenylmethane diisocyanates (MDI), hexamethylene diisocyanate, isophorone diisocyanate Ester, di-2-ethylhexylphosphine oxide (cyclohexyl) diisocyanate (HMDI), trans- 1,4- cyclohexane diisocyanate (CHDI), to two isocyanide of benzene Acid esters, lysine diisocyanate, terephthalylidene diisocyanate, 1,5- pentamethylene diisocyanate, to tetramethyl two Toluene di-isocyanate(TDI), tetramethylxylene diisocyanate and its mixture.

In the present invention, in step (ii), polymerization catalyst is selected from: triethylenediamine, dibutyl tin dilaurate, Stannous octoate and its mixture.

In the present invention, in step (ii), prepolymerized temperature is 50-200 DEG C, preferably 65-95 DEG C, and prepolymerization Time be 1-5h.

In the present invention, in step (ii), for the reaction-ure mixture of 10mL to 2L, microwave irradiation power is 100- 800W。

In the present invention, in step (iii), cahin extension agent is selected from ethylene glycol, 1,3-PD, 1,4-butanediol, Isosorbide-5-Nitrae- Hexylene glycol, 1,4- cyclohexanediol, 1,6-HD, 1,8- ethohexadiol, 1,9- nonanediol, 1,10- decanediol, to diphenyl second two Alcohol, rosin dimethanol (colophony dimethol), ethylenediamine, propane diamine, butanediamine, hexamethylene diamine, cyclohexanediamine and its mixed Close object；

In the present invention, in step (iii), the temperature of polymerization is 50-250 DEG C, and the time polymerizeing is 1-5h, excellent Select 2-3h.

In the present invention, step (i)-(iii) in the presence of a solvent, wherein the solvent is selected from toluene, diformazan Benzene, tetrahydrofuran, chloroform, N,N-dimethylformamide, ethyl acetate, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide and its mixed Close object.