CN108976380A - A kind of fast molded thermoplastic polyurethane of low melting point and its preparation method - Google Patents
A kind of fast molded thermoplastic polyurethane of low melting point and its preparation method Download PDFInfo
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- CN108976380A CN108976380A CN201810695122.5A CN201810695122A CN108976380A CN 108976380 A CN108976380 A CN 108976380A CN 201810695122 A CN201810695122 A CN 201810695122A CN 108976380 A CN108976380 A CN 108976380A
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- thermoplastic polyurethane
- melting point
- low melting
- molded thermoplastic
- fast
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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
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- 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
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
-
- 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
- C08G18/65—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
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/06—Polyurethanes from polyesters
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The present invention relates to a kind of fast molded thermoplastic polyurethane of low melting point and its preparation methods.Its thermoplastic polyurethane is characterized in that containing following components: 1) polyester polyol, and it is 84-97.4wt% that the polyester polyol, which is by dicarboxylic acids and small molecular alcohol constituent component mass ratio,；2) isocyanates, constituent mass accounting are 2.6-13wt%；3) catalyst, constituent mass ratio are 0-0.03wt%；4) antioxidant, constituent mass ratio are 0-0.5wt%.Preparation method, it is characterised in that steps are as follows: polyalcohol, isocyanates, chain extender, catalyst, antioxidant are uniformly mixed, and are squeezed out and are prepared through double screw extruder, and reaction system isocyanate index is 0.8~1.00, and extrusion process temperature is 100~250 DEG C.The fast molded thermoplastic polyurethane of low melting point produced by the present invention has the advantages that fusing point is low, molding is fast, with high hardness.
Description
Technical field
The present invention is polyurethane field, is related to a kind of fast molded thermoplastic polyurethane of low melting point and its preparation method.
Background technique
Thermoplastic polyurethane (Thermoplastic Polyurethane, TPU) be it is a kind of can reprocessabilty thermoplasticity
Property body, there are the performances such as high-intensitive, high resiliency and high abrasion, have both the feature of rubber and plastics, processing method include squeeze out, note
Modeling, dissolution etc..It is widely used in the fields such as civilian, building, medical treatment, aviation, industry, military project.
Conventional thermoplastic's melt polyurethane temperature is higher, and generally greater than 100 DEG C.And heat lower for partial melting temperature
Plastic polyurethane, crystalline rate is then relatively slow, and crystallization time is more than 20 minutes.Therefore conventional thermoplastic's polyurethane is difficult to have both low
The characteristics of fusing point forms fastly, it is difficult to meet the fast manufacture field application of low temperature.
A kind of crystalline polyurethane composition has been used in patent CN107406568A announcement, and polyol used is that molecular weight is
The butanediol succinate of 4000-6000, fusing point are 80-130 DEG C, and the recrystallization time is less than 5min, have fast molding spy
Point, but its fusing point is higher than 80 DEG C, and the low temperature lower than 80 DEG C cannot be achieved and form fastly.
A kind of soft height rebound low melting point thermoplastic polyurethane elastomer of patent CN108070069A announcement, it is used
Polyol is the polyester polyol of molecular weight 500-4000, and small molecule used is 1,4-butanediol, 1,6 hexylene glycols and small molecular alcohol,
Its fusing point is 80-150 DEG C, the hardness 45-80A of product, and since its fusing point is higher than 80 DEG C, the low temperature that cannot be achieved lower than 80 DEG C is fast
Molding, simultaneously because hardness is very low (45-80A), modulus needed for cannot reaching 95A hardness can not meet supporting role, therefore nothing
Method is applied to medical plate and port treasured field.
Summary of the invention
Present invention aim to address prior art thermoplastic polyurethanes cannot have both low melting point molding defect fastly, provides
A kind of fast molded thermoplastic polyurethane of low melting point and its preparation method, fusing point is low, molding is fast, hardness is high, can satisfy low temperature and adds fastly
The application of work field.
The present invention is achieved by the following technical solution:
I.e. a kind of fast molded thermoplastic polyurethane of low melting point, it is characterised in that contain following components:
1) polyester polyol, the polyester polyol are made of dicarboxylic acids and small molecular alcohol, wherein dicarboxylic acids knot
Structure formula is HOOC (CH2)nCOOH, n 4,8 and 10, small molecular alcohol are butanediol or hexylene glycol；The group sub-prime of the polyester polyol
Amount is than being 84-97.4wt%；
2) isocyanates, constituent mass accounting are 2.6-13wt%；
3) catalyst, institute's catalyst are metallic catalyst, and constituent mass ratio is 0-0.03wt%；
4) antioxidant, the antioxidant are hindered phenol antioxygen, and constituent mass ratio is 0-0.5wt%.
The present invention is additionally provided with chain extender, and the constituent mass ratio of chain extender is 0~3wt%.
Further, the constituent mass of chain extender of the invention is than preferred 0-2wt%.
Chain extender component quality accounting of the invention can also be 0wt%.I.e. thermoplastic polyurethane containing polyester polyol with it is different
Cyanate is free of chain extender component.
Polyester polyol molecule amount of the invention is 4000-6000g/mol.
Polyester polyol of the invention is polyadipate hexylene glycol ester, polydiethylene glycol sebacate, poly- decanedioic acid hexylene glycol
Ester, poly- lauric acid butanediol ester, one or more mixing in poly- lauric acid hexylene glycol ester.
Further, the preferred polyadipate hexylene glycol ester of polyester polyol of the invention, polydiethylene glycol sebacate, poly- ten
One or more mixing in two carbonic acid butanediol esters.
Isocyanates of the invention is 4,4- methyl diphenylene diisocyanate, hexamethylene diisocyanate, 4,4- bis-
One or more mixing in diphenylmethane diisocyanate, toluene di-isocyanate(TDI).
Further, polyester polyol of the invention preferably 4,4- methyl diphenylene diisocyanate or hexa-methylene two are different
Cyanate or both mixing.
Chain extender of the invention is ethylene glycol, 1,3- propylene glycol, 1,4- butanediol, one or more mixed in 1,6-HD
It closes.
Further, the preferred 1,4-butanediol of chain extender of the invention or 1,6- hexylene glycol or both mixing.
Further, catalyst of the invention is the metallic catalysts such as organotin, organo-bismuth.
Further, antioxidant of the invention is the hindered phenol antioxygens such as 1010,1076.
A kind of preparation method of the fast molded thermoplastic polyurethane of low melting point, it is characterised in that steps are as follows: by polyalcohol, different
Cyanate, chain extender, catalyst, antioxidant are uniformly mixed, and are squeezed out and are prepared through double screw extruder, and reaction system isocyanates refers to
Number is 0.8~1.00, and extrusion process temperature is 100~250 DEG C.
Further, reaction system isocyanate index preferably 0.85~0.95 of the invention, extrusion process temperature is preferred
130-200℃。
Present invention employs middle long carbochain biatomic acid (adipic acid, decanedioic acid and dodecanedioic acid) and linear diols (1,
4- butanediol and 1,6 hexylene glycols) liner polyesterdiols crystallized with low melting point, fastly are prepared, with such polyol and isocyanide
Acid esters and chain extender component prepare the thermoplastic polyurethane with low melting point, fast molding and high rigidity.
The fast molded thermoplastic polyurethane of low melting point produced by the present invention has the advantages that fusing point is low, molding is fast, with high hardness.This
Invent the fast molded thermoplastic polyurethane of low melting point obtained, melting temperature TmLess than or equal to 75 DEG C；Its DSC crystallization temperature Tc
More than or equal to 30 DEG C；Its molding time is less than or equal to 4min；Its Shore hardness is more than or equal to 95A.
Specific embodiment
The embodiment of technical solution of the present invention is described in detail below.Following embodiment is only used for clearly
Illustrate technical solution of the present invention, therefore be only used as example, and not intended to limit the protection scope of the present invention.It should be noted that
, unless otherwise indicated, technical term or scientific term used in this application should be fields technology people of the present invention
The ordinary meaning that member is understood.
Embodiment 1
Polyadipate hexylene glycol ester, the 5.30wt%4 for being 4000g/mol by 94.39wt% number-average molecular weight, 4- diphenyl
Methane diisocyanate, 0.01wt% stannous octoate and 0.30%1010 are uniformly mixed, and through twin-screw reactive extrursion, TPU is made
Adhesive.
Embodiment 2
Decanedioic acid butanediol ester, the 5.28wt%4 for being 4000g/mol by 94.3wt% number-average molecular weight, 4- diphenylmethyl
Alkane diisocyanate, 0.02wt% stannous octoate and 0.4%1076 are uniformly mixed, and through twin-screw reactive extrursion, TPU gluing is made
Agent.
Embodiment 3
Decanedioic acid hexylene glycol ester, the 5.28wt%4 for being 4000g/mol by 94.2wt% number-average molecular weight, 4- diphenylmethyl
Alkane diisocyanate, 0.02wt% bismuth neodecanoate and 0.5%1010 are uniformly mixed, and through twin-screw reactive extrursion, TPU gluing is made
Agent.
Embodiment 4
Dodecanedioic acid butanediol ester, the 5.27wt%4 for being 4000g/mol by 94.2wt% number-average molecular weight, 4- hexichol
Dicyclohexylmethane diisocyanate, 0.03wt% bismuth neodecanoate and 0.5%1076 are uniformly mixed, and through twin-screw reactive extrursion, TPU is made
Adhesive.
Embodiment 5
By six Asia of poly- dodecanedioic acid acid hexylene glycol ester and 2.6wt% that 97.4wt% number-average molecular weight is 6000g/mol
Methyl diisocyanate is uniformly mixed by isocyanates, does not add catalyst and antioxidant, through twin-screw reactive extrursion, is made
TPU adhesive.
Embodiment 6
The polydiethylene glycol sebacate for being 5000g/mol by 89.67wt% number-average molecular weight, 8.5wt%4,4- diphenyl
Methane diisocyanate, 1.5wt%1,4- butanediol, 0.03wt% stannous octoate and 0.3%1010 are uniformly mixed, through twin-screw
TPU adhesive is made in reactive extrursion.
Comparative example 1
Poly adipate succinic acid ester, the 5.30wt%4 for being 4000g/mol by 94.39wt% number-average molecular weight, 4- diphenyl
Methane diisocyanate, 0.01wt% stannous octoate and 0.30%1010 are uniformly mixed, and through twin-screw reactive extrursion, TPU is made
Adhesive.
Fusing point, crystal property, molding time and hardness test are carried out to above-mentioned TPU adhesive samples respectively.Pass through capillary
The fusing point of pipe rheometer test sample, DSC test sample crystallization temperature, the molding time of sample is assessed with hardness rise method；
| Test item | Fusing point/DEG C | Crystallization temperature/DEG C | Molding time | Hardness |
| Test method | Capillary rheometer | DSC | Hardness rise method | Shore A |
| Embodiment 1 | 57.4 | 36.4 | 3min 50s | 96 |
| Embodiment 2 | 65.7 | 42.5 | 2min 10s | 97 |
| Embodiment 3 | 67.6 | 44.8 | 1min 30s | 97 |
| Embodiment 4 | 66.6 | 43.3 | 1min45s | 97 |
| Embodiment 5 | 71.5 | 50.3 | 50s | 98 |
| Embodiment 6 | 72.4 | 40.3 | 2min 20s | 97 |
| Comparative example 1 | 53.6 | 24.5 | 6min 10s | 96 |
The above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；Although referring to aforementioned each reality
Applying example, invention is explained in detail, those skilled in the art should understand that: it still can be to aforementioned each
Technical solution documented by embodiment is modified, or equivalent substitution of some or all of the technical features；And
These are modified or replaceed, the range for technical solution of various embodiments of the present invention that it does not separate the essence of the corresponding technical solution,
It should all cover within the scope of the claims and the description of the invention.
Claims (10)
1. a kind of fast molded thermoplastic polyurethane of low melting point, it is characterised in that contain following components:
1) polyester polyol, the polyester polyol are made of dicarboxylic acids and small molecular alcohol, wherein dicarboxylic acids structural formula
For HOOC (CH2) nCOOH, n 4,8 and 10, small molecular alcohol is butanediol or hexylene glycol；The constituent mass ratio of the polyester polyol
For 84-97.4wt%；
2) isocyanates, constituent mass accounting are 2.6-13wt%；
3) catalyst, institute's catalyst are metallic catalyst, and constituent mass ratio is 0-0.03wt%；
4) antioxidant, the antioxidant are hindered phenol antioxygen, and constituent mass ratio is 0-0.5wt%.
2. the fast molded thermoplastic polyurethane of low melting point according to claim 1, it is characterised in that be additionally provided with chain extender, chain extension
The constituent mass ratio of agent is 0~3wt%.
3. the fast molded thermoplastic polyurethane of low melting point according to claim 1, it is characterised in that polyester polyol molecule amount
For 4000-6000g/mol.
4. the fast molded thermoplastic polyurethane of low melting point according to claim 1 or 3, it is characterised in that polyester polyol is poly-
Adipic acid hexylene glycol ester, polydiethylene glycol sebacate, poly- decanedioic acid hexylene glycol ester, poly- lauric acid butanediol ester, poly- 12 carbon
One of sour hexylene glycol ester or a variety of mixing.
5. the fast molded thermoplastic polyurethane of low melting point according to claim 4, it is characterised in that isocyanates 4,4- bis-
Methylenebis phenyl isocyanate, hexamethylene diisocyanate, 4,4- dicyclohexyl methyl hydride diisocyanate, toluene diisocynate
One or more mixing in ester.
6. the fast molded thermoplastic polyurethane of low melting point according to claim 2, it is characterised in that chain extender be ethylene glycol, 1,
One of 3-propanediol, 1,4- butanediol, 1,6-HD or a variety of mixing.
7. the fast molded thermoplastic polyurethane of low melting point according to claim 1, it is characterised in that catalyst be organotin or
Organo-bismuth.
8. the fast molded thermoplastic polyurethane of low melting point according to claim 1, it is characterised in that antioxidant be 1010 or
1076。
9. a kind of preparation method of the fast molded thermoplastic polyurethane of low melting point, it is characterised in that steps are as follows: by polyalcohol, isocyanic acid
Ester, chain extender, catalyst, antioxidant are uniformly mixed, and are squeezed out and are prepared through double screw extruder, and reaction system isocyanate index is
0.8~1.00, extrusion process temperature is 100~250 DEG C.
10. the preparation method of the fast molded thermoplastic polyurethane of low melting point according to claim 9, it is characterised in that preferred isocyanic acid
Ester index is 0.85~0.95, and extrusion process temperature is 130-200 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810695122.5A CN108976380A (en) | 2018-06-29 | 2018-06-29 | A kind of fast molded thermoplastic polyurethane of low melting point and its preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810695122.5A CN108976380A (en) | 2018-06-29 | 2018-06-29 | A kind of fast molded thermoplastic polyurethane of low melting point and its preparation method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108976380A true CN108976380A (en) | 2018-12-11 |
Family
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| CN201810695122.5A Withdrawn CN108976380A (en) | 2018-06-29 | 2018-06-29 | A kind of fast molded thermoplastic polyurethane of low melting point and its preparation method |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110804160A (en) * | 2019-10-10 | 2020-02-18 | 江苏华大新材料有限公司 | Waterborne polyurethane for vacuum forming adhesive and preparation method thereof |
| CN111979597A (en) * | 2020-09-02 | 2020-11-24 | 浙江吉仑高分子材料股份有限公司 | Method for preparing thermal fuse |
| CN113930183A (en) * | 2020-06-29 | 2022-01-14 | 德莎欧洲股份公司 | Storage-stable reactive pressure-sensitive adhesive tape |
| CN114149559A (en) * | 2021-12-07 | 2022-03-08 | 黎明化工研究设计院有限责任公司 | High-strength and high-elongation thermoplastic polyurethane material and preparation method and application thereof |
| CN114479742A (en) * | 2022-02-22 | 2022-05-13 | 河北邦泰氨纶科技有限公司 | Bio-based high-crystallinity water-based polyurethane adhesive for shoes and preparation process thereof |
| CN114774060A (en) * | 2022-05-11 | 2022-07-22 | 河北邦泰氨纶科技有限公司 | Rapid crystallization hot melt adhesive for port materials and preparation method thereof |
-
2018
- 2018-06-29 CN CN201810695122.5A patent/CN108976380A/en not_active Withdrawn
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110804160A (en) * | 2019-10-10 | 2020-02-18 | 江苏华大新材料有限公司 | Waterborne polyurethane for vacuum forming adhesive and preparation method thereof |
| CN113930183A (en) * | 2020-06-29 | 2022-01-14 | 德莎欧洲股份公司 | Storage-stable reactive pressure-sensitive adhesive tape |
| US11926769B2 (en) | 2020-06-29 | 2024-03-12 | Tesa Se | Storage-stable, reactive, pressure-sensitive adhesive tape |
| CN111979597A (en) * | 2020-09-02 | 2020-11-24 | 浙江吉仑高分子材料股份有限公司 | Method for preparing thermal fuse |
| CN111979597B (en) * | 2020-09-02 | 2023-06-23 | 吴键儒 | Method for preparing thermal fuse |
| CN114149559A (en) * | 2021-12-07 | 2022-03-08 | 黎明化工研究设计院有限责任公司 | High-strength and high-elongation thermoplastic polyurethane material and preparation method and application thereof |
| CN114149559B (en) * | 2021-12-07 | 2023-12-15 | 黎明化工研究设计院有限责任公司 | High-strength high-elongation thermoplastic polyurethane material and preparation method and application thereof |
| CN114479742A (en) * | 2022-02-22 | 2022-05-13 | 河北邦泰氨纶科技有限公司 | Bio-based high-crystallinity water-based polyurethane adhesive for shoes and preparation process thereof |
| CN114479742B (en) * | 2022-02-22 | 2023-10-20 | 河北邦泰氨纶科技有限公司 | Bio-based high-crystallinity aqueous polyurethane adhesive for shoes and preparation process thereof |
| CN114774060A (en) * | 2022-05-11 | 2022-07-22 | 河北邦泰氨纶科技有限公司 | Rapid crystallization hot melt adhesive for port materials and preparation method thereof |
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