CN107903369B - Preparation method and application of organic silicon-polyurethane thermoplastic elastomer - Google Patents
Preparation method and application of organic silicon-polyurethane thermoplastic elastomer Download PDFInfo
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- CN107903369B CN107903369B CN201711187447.4A CN201711187447A CN107903369B CN 107903369 B CN107903369 B CN 107903369B CN 201711187447 A CN201711187447 A CN 201711187447A CN 107903369 B CN107903369 B CN 107903369B
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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
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- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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- 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
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- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
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Abstract
本发明公开一种有机硅‑聚氨酯热塑性弹性体的制备方法，该制备方法包括如下步骤：Ⅰ、在50～120℃温度下，通过将大分子有机硅二元醇、二异氰酸酯、增容剂按照一定的方式进行混合，反应得到异氰酸酯基封端的预聚体；Ⅱ、将步骤Ⅰ所得预聚体与小分子扩链剂均匀混合，并将混合物浇注后熟化。所制备的有机硅‑聚氨酯热塑性弹性体除了具有良好的力学性能外，还具有优异的疏水性能和耐低温性能。The invention discloses a preparation method of an organosilicon-polyurethane thermoplastic elastomer. The preparation method comprises the following steps: 1. At a temperature of 50-120 DEG C, by mixing macromolecular organosilicon diol, diisocyanate and compatibilizer according to Mixing in a certain way to obtain the isocyanate group-terminated prepolymer; II. The prepolymer obtained in step I and the small molecule chain extender are uniformly mixed, and the mixture is cast and aged. In addition to good mechanical properties, the prepared silicone-polyurethane thermoplastic elastomer also has excellent hydrophobic properties and low temperature resistance.
Description
The technical field is as follows:
the invention belongs to the field of elastomer materials, and further relates to a preparation method of an organic silicon-polyurethane thermoplastic elastomer.
Background art:
thermoplastic polyurethane elastomer (TPU) is a comprehensive material composed of soft and hard segments which are thermodynamically incompatible and has excellent properties such as high strength, high toughness, high elasticity and the like, and is widely used in various industries.
Organosilicon is a general name of a plurality of high molecular compounds containing silicon elements, wherein polyorganosiloxane is most widely applied, and the polyorganosiloxane has good thermal stability, oxidation resistance, good water repellency, low glass transition temperature, low surface energy and excellent physiological inertia. Polydimethylsiloxane (PDMS) is one of the most common polyorganosiloxanes, and introduction of PDMS into TPU to make silicon-containing TPU has been the most studied. However, PDMS has low polarity, small solubility parameter and poor compatibility with other components, so that the prepared silicon-containing TPU has poor physical and mechanical properties.
In the prior research on the preparation of silicon-containing TPU, the compatibility between polyorganosiloxane and hard segment is improved basically by modifying the soft segment, including the following two aspects:
firstly, the preparation, composition and performance of a polysiloxane-containing polyurethane elastomer are disclosed in U.S. Pat. No. 4, 006313254, 1 by adding another soft segment (generally polyether, polyester, polycarbonate, etc. macrodiol) with higher solubility parameter, wherein MDI/BDO is used as a hard segment, at least one polysiloxane macrodiol and at least one polyether/polycarbonate macrodiol are used as soft segments, the physical and mechanical properties of the obtained product are general, and the operation process of the invention is complex.
Secondly, by modifying the polyorganosiloxane intramolecularly (such as preparing PEO-PMDS-PEO, PCL-PDMS-PCL, introducing chloropropyl, nitrile ethyl and other side groups into PDMS molecules), for example, Chinese patent CN104448231A discloses a preparation method, a product and application of a polyether organic silicon block polyurethane material.
The compatibility between the polyorganosiloxane and the hard segment is improved by modifying the hard segment, the phase separation degree between the hard segment and the soft segment is reduced, and the physical and mechanical properties of the prepared silicon-containing TPU are improved.
Disclosure of Invention
The invention aims to provide a preparation method of an organic silicon-polyurethane thermoplastic elastomer, which changes the characteristics of a hard segment by selecting a compatibilizer with a special structure and improves the compatibility between organic silicon and the hard segment by optimizing a preparation process, so that an organic silicon-polyurethane thermoplastic elastomer product with good mechanical property is obtained, and the product also has excellent hydrophobic property and low-temperature resistance.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
a preparation method of a silicone-polyurethane thermoplastic elastomer comprises the following steps:
i, mixing macromolecular organic silicon diol, a compatibilizer and diisocyanate according to a certain mode at the temperature of 50-120 ℃ to react to obtain an isocyanate-terminated prepolymer;
II, uniformly mixing the prepolymer obtained in the step I with a small molecular chain extender, pouring the mixture and curing to obtain the organic silicon-polyurethane thermoplastic elastomer;
as a preferred technical solution, the mixing manner in step i is any one of the following manners, preferably manner 3):
mode 1) sequentially and gradually adding macromolecular organic silicon dihydric alcohol and a compatibilizer into diisocyanate;
mode 2) adding diisocyanate and a compatibilizer gradually into macromolecular organic silicon diol in sequence;
mode 3) firstly, uniformly mixing macromolecular organic silicon diol and a compatibilizer, and then gradually adding the mixture into diisocyanate; the mixing mode is adopted to change the characteristics of the hard segment of the organic silicon-polyurethane thermoplastic elastomer material, and the solubility parameter of the hard segment can be reduced to a greater extent, so that the compatibility between the soft segment and the hard segment of the organic polysiloxane is improved, and the organic silicon-polyurethane thermoplastic elastomer product with good mechanical property is obtained.
Mode 4) first uniformly mixing the macromolecular silicone glycol and the compatibilizer to obtain a mixture, and then gradually adding the diisocyanate to the mixture.
In the invention, the macromolecular organic silicon dihydric alcohol is hydroxyl-terminated polysiloxane and is any one of molecular structures shown in a structural formula I:
n in the structural formula I is an integer of 1-50, and Q 1 And Q 2 is-CH 3 、
Any one of the above; x is the following a 1 ～a 9 Any one of the structures, a 1 )-C 3 H 6 -OH；a 2 )-C 4 H 8 -OH；a 3 )-C 5 H 10 -OH；a 4 )-C 6 H 12 -OH；a 5 )-C 3 H 6 OC 2 H 4 -OH；a 6 )-C 3 H 6 OCH 2 CH(OH)CH 2 OCH 3 ；a 7 )
a 8 )
a 9 )
Preferably, in the structural formula I, n is an integer of 2-20, and X is a 1 、a 3 、a 5 Any one of the structures.
In the invention, the compatibilizer is at least one of the following molecular structures, preferably b 3 、b 4 、b 5 、b 6 、b 7 At least one of (1).
b 1 )HOCH 2 CH 2 OCH 2 CH 2 OH；b 2 )HOCH(CH 3 )CH 2 OCH 2 CH(CH 3 )OH；
b 3 )
b 4 )
b 5 )
b 6 )
b 7 )
In the present invention, the diisocyanate is at least one of aliphatic, alicyclic or aromatic diisocyanates, including at least one of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, p-phenylene diisocyanate, naphthalene diisocyanate, 1, 4-cyclohexane diisocyanate, xylylene diisocyanate, cyclohexanedimethylene diisocyanate, trimethyl-1, 6-hexamethylene diisocyanate, tetramethyl-m-xylylene diisocyanate, norbornane diisocyanate, dimethylbiphenyl diisocyanate, methylcyclohexyl diisocyanate, dimethyldiphenylmethane diisocyanate, lysine diisocyanate, preferably toluene diisocyanate, diphenylmethane diisocyanate, dimethylmethane diisocyanate, and dimethylmethane diisocyanate, and dimethylmethane diisocyanate, and a, At least one of isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, and p-phenylene diisocyanate.
In the present invention, the small-molecule chain extender is at least one of ethylene glycol, 1, 4-butanediol, 1, 2-propanediol, neopentyl glycol, methyl propanediol, 1, 6-hexanediol, 1, 3-propanediol, butylethylpropanediol, diethylpentanediol, 3-methyl-1, 5-pentanediol, 1, 3-butanediol, 1, 2-butanediol, 2, 3-butanediol, trimethylpentanediol, 1, 5-pentanediol, 1, 2-pentanediol, preferably ethylene glycol, 1, 4-butanediol, 1, 6-hexanediol, 1, 3-propanediol, and 1, 5-pentanediol.
In the invention, the mass fraction of the macromolecular organic silicon diol in the raw materials for preparing the organic silicon-polyurethane thermoplastic elastomer is 42-69 wt%, preferably 50-60 wt%; the mass fraction of the compatibilizer is 1-15 wt%, preferably 5-10 wt%; the mass fraction of the diisocyanate is 10-40 wt%, preferably 20-30 wt%; the mass fraction of the micromolecule chain extender is 3-20 wt%, preferably 5-10 wt%; based on the total amount of the raw materials.
In the invention, the molar ratio of the isocyanic acid radical to the active hydrogen in the raw materials for preparing the organic silicon-polyurethane thermoplastic elastomer is 0.8-1.3, preferably 0.9-1.1.
The organic silicon-polyurethane thermoplastic elastomer has tensile strength of more than 20MPa, elongation at break of more than 500 percent, good mechanical property, static water contact angle of more than 110 degrees and glass transition temperature of less than-90 ℃, excellent hydrophobic property and low temperature resistance, and can be used as biomedical materials, such as in an intra-aortic balloon, an artificial heart, a catheter and a blood vessel.
The positive progress effects of the invention are as follows:
1. the compatibility between polyorganosiloxane in the prepared organic silicon-polyurethane thermoplastic elastomer and the hard segment is improved by changing the structure of the hard segment, so that the performance of the organic silicon-polyurethane thermoplastic elastomer is improved;
2. the structure of the hard segment, including polarity, symmetry and the like, is changed mainly by selecting different compatibilizers, so that the solubility parameter and the crystallization behavior of the hard segment are changed, and the purposes of improving the compatibility between polyorganosiloxane and the hard segment and reducing the phase separation degree between a soft segment and a hard segment are achieved;
3. the prepared organic silicon-polyurethane thermoplastic elastomer has good physical and mechanical properties, excellent hydrophobic property and low temperature resistance, and can be used as biomedical materials.
The specific implementation method comprises the following steps:
the present invention will be described in further detail with reference to specific embodiments, but it should not be construed that the scope of the present invention is limited to the following examples. Various substitutions and alterations can be made by those skilled in the art and by conventional means without departing from the spirit of the method of the invention described above.
Example 1
Raw materials for preparing the silicone-polyurethane thermoplastic elastomer:
1) macromolecular silicone glycol:
wherein Q 1 And Q 2 is-CH 3 N is 50 and X is
shin-Etsu chemical industry Co., Ltd., KF 6003;
2) compatibilizer:
HOCH 2 CH 2 OCH 2 CH 2 OH
3) diisocyanate: 1, 4-cyclohexane diisocyanate;
4) small molecule chain extender: neopentyl glycol, methyl propylene glycol;
i, mixing macromolecular organic silicon diol, a compatibilizer and diisocyanate according to a certain mode at the temperature of 50 ℃ to react to obtain an isocyanate-terminated prepolymer;
II, uniformly mixing the prepolymer obtained in the step I with a small molecular chain extender, pouring the mixture and curing to obtain the organic silicon-polyurethane thermoplastic elastomer;
the mixing mode in the step I is selected from a mode 1): sequentially and gradually adding macromolecular organic silicon dihydric alcohol and a compatibilizer into diisocyanate;
in the raw materials for preparing the organic silicon-polyurethane thermoplastic elastomer, the mass fraction of macromolecular organic silicon diol is 69 wt%, the mass fraction of compatibilizer is 1 wt%, the mass fraction of diisocyanate is 10 wt%, and the mass fraction of micromolecular chain extender is 20 wt%, based on the total amount of the raw materials. The molar ratio of isocyanic acid radical to active hydrogen in the raw material is 0.8, and the mass ratio of neopentyl glycol to methyl propylene glycol in the micromolecular chain extender is 1: 2;
the properties of the silicone-polyurethane thermoplastic elastomer prepared are shown in table 1.
Example 2
Raw materials for preparing the organic silicon-polyurethane thermoplastic elastomer:
1) macromolecular silicone glycol:
wherein Q 1 And Q 2 Is composed of
n is 1, X is-C 3 H 6 -OH, shin-Etsu chemical Co., Ltd, X-22-160 AS;
2) a compatibilizer:
HOCH(CH 3 )CH 2 OCH 2 CH(CH 3 )OH
3) diisocyanate: xylylene diisocyanate, cyclohexanedimethylene diisocyanate;
4) small-molecule chain extender: butyl ethyl propylene glycol;
i, mixing macromolecular organic silicon diol, a compatibilizer and diisocyanate according to a certain mode at the temperature of 100 ℃ to react to obtain an isocyanate-terminated prepolymer;
II, uniformly mixing the prepolymer obtained in the step I with a small molecular chain extender, pouring the mixture and curing to obtain the organic silicon-polyurethane thermoplastic elastomer;
the mixing mode in the step I is selected from a mode 2): sequentially and gradually adding diisocyanate and a compatibilizer into the macromolecular organic silicon diol;
in the raw materials for preparing the organic silicon-polyurethane thermoplastic elastomer, the mass fraction of macromolecular organic silicon diol is 42 wt%, the mass fraction of a compatibilizer is 15 wt%, the mass fraction of diisocyanate is 40 wt%, and the mass fraction of a micromolecular chain extender is 3 wt%, based on the total amount of the raw materials. The molar ratio of isocyanic acid radical to active hydrogen in the raw materials is 1.3, and the mass ratio of the xylylene diisocyanate to the cyclohexane dimethylene diisocyanate in the diisocyanate is 1: 0.5;
the properties of the silicone-polyurethane thermoplastic elastomer prepared are shown in table 1.
Example 3
Raw materials for preparing the silicone-polyurethane thermoplastic elastomer:
1) macromolecular silicone glycol:
wherein Q 1 And Q 2 is-CH 3 N is 25 and X is-C 4 H 8 -OH, shin & shin-Etsu chemical industries co., KF 6002;
2) compatibilizer:
compatibilizer 1: HOCH (CH) 3 )CH 2 OCH 2 CH(CH 3 )OH
Compatibilizer 2:
SEPPIC corporation, france, Dianol 320;
3) diisocyanate: hexamethylene diisocyanate;
4) small-molecule chain extender: ethylene glycol;
i, mixing macromolecular organic silicon diol, a compatibilizer and diisocyanate according to a certain mode at the temperature of 100 ℃ to react to obtain an isocyanate-terminated prepolymer;
II, uniformly mixing the prepolymer obtained in the step I with a small molecular chain extender, pouring the mixture and curing to obtain the organic silicon-polyurethane thermoplastic elastomer;
the mixing mode in the step I is selected from a mode 2): sequentially and gradually adding diisocyanate and a compatibilizer into the macromolecular organic silicon diol;
in the raw materials for preparing the organic silicon-polyurethane thermoplastic elastomer, the mass fraction of macromolecular organic silicon diol is 65 wt%, the mass fraction of a compatibilizer is 10 wt%, the mass fraction of diisocyanate is 20 wt%, and the mass fraction of a micromolecular chain extender is 5 wt%, based on the total amount of the raw materials. The molar ratio of isocyanic acid radical to active hydrogen in the raw material is 1.1, and the mass ratio of a compatibilizer 1 to a compatibilizer 2 in the compatibilizer is 1: 0.4;
the properties of the silicone-polyurethane thermoplastic elastomer prepared are shown in table 1.
Example 4
Raw materials for preparing the silicone-polyurethane thermoplastic elastomer:
1) macromolecular silicone glycol:
wherein Q 1 And Q 2 is-CH 3 N is 10, X is-C 3 H 6 OC 2 H 4 -OH, shin & shin-Etsu chemical industries co., KF 6000;
2) compatibilizer:
SEPPIC corporation, france, Dianol 220;
3) diisocyanate: diphenylmethane diisocyanate;
4) small-molecule chain extender: 1, 4-butanediol;
i, mixing macromolecular organic silicon diol, a compatibilizer and diisocyanate according to a certain mode at the temperature of 90 ℃, and reacting to obtain an isocyanate-terminated prepolymer;
II, uniformly mixing the prepolymer obtained in the step I with a small molecular chain extender, pouring the mixture and curing to obtain the organic silicon-polyurethane thermoplastic elastomer;
the mixing mode in the step I is selected from a mode 3): firstly, uniformly mixing macromolecular organic silicon diol and a compatibilizer, and then gradually adding the mixture into diisocyanate;
in the raw materials for preparing the organic silicon-polyurethane thermoplastic elastomer, the mass fraction of macromolecular organic silicon diol is 55 wt%, the mass fraction of a compatibilizer is 10 wt%, the mass fraction of dicyanate is 25 wt%, and the mass fraction of a micromolecular chain extender is 10 wt%, based on the total amount of the raw materials. The molar ratio of isocyanic acid radical to active hydrogen in the raw material is 1;
the properties of the silicone-polyurethane thermoplastic elastomer prepared are shown in table 1.
Comparative example 1
Raw materials for preparing the silicone-polyurethane thermoplastic elastomer:
1) macromolecular silicone glycol:
wherein Q 1 And Q 2 is-CH 3 N is 10, X is-C 3 H 6 OC 2 H 4 -OH, shin & shin-Etsu chemical industries co., KF 6000;
2) diisocyanate: diphenylmethane diisocyanate;
3) small-molecule chain extender: 1, 4-butanediol;
i, mixing macromolecular organic silicon diol and diisocyanate according to a certain mode at the temperature of 90 ℃, and reacting to obtain an isocyanate-terminated prepolymer;
II, uniformly mixing the prepolymer obtained in the step I with a small molecular chain extender, pouring the mixture and curing to obtain the organic silicon-polyurethane thermoplastic elastomer;
the mixing mode in the step I is as follows: gradually adding macromolecular organic silicon diol into diisocyanate;
in the raw materials for preparing the organic silicon-polyurethane thermoplastic elastomer, the mass fraction of macromolecular organic silicon dihydric alcohol is 55 wt%, the mass fraction of dicyanate is 25 wt%, and the mass fraction of a micromolecular chain extender is 20 wt%, based on the total amount of the raw materials. The molar ratio of isocyanic acid radical to active hydrogen in the raw material is 1;
the properties of the silicone-polyurethane thermoplastic elastomer prepared are shown in table 1.
Example 5
Raw materials for preparing the silicone-polyurethane thermoplastic elastomer:
1) macromolecular silicone glycol:
wherein Q 1 And Q 2 is-CH 3 N is 2, X is-C 3 H 6 OCH 2 CH(OH)CH 2 OCH 3 X-22-4952, shin-Etsu chemical Co., Ltd;
2) a compatibilizer:
BASF corporation, HPN;
3) diisocyanate: toluene diisocyanate, hexamethylene diisocyanate;
4) small-molecule chain extender: ethylene glycol, 1, 6-hexanediol;
i, mixing macromolecular organic silicon diol, a compatibilizer and diisocyanate according to a certain mode at the temperature of 120 ℃ to react to obtain an isocyanate-terminated prepolymer;
II, uniformly mixing the prepolymer obtained in the step I with a small molecular chain extender, pouring the mixture and curing to obtain the organic silicon-polyurethane thermoplastic elastomer;
the mixing mode in the step I is selected from a mode 4): firstly, uniformly mixing macromolecular organic silicon diol and a compatibilizer to obtain a mixture, and then gradually adding diisocyanate into the mixture;
in the raw materials for preparing the organic silicon-polyurethane thermoplastic elastomer, the mass fraction of macromolecular organic silicon dihydric alcohol is 60 wt%, the mass fraction of a compatibilizer is 5 wt%, the mass fraction of dicyanate is 30 wt%, and the mass fraction of a micromolecular chain extender is 5 wt%, based on the total amount of the raw materials. The molar ratio of isocyanic acid radical to active hydrogen in the raw material is 1.1, the mass ratio of toluene diisocyanate to hexamethylene diisocyanate in diisocyanate is 1:1, and the mass ratio of ethylene glycol to 1, 6-hexanediol in the micromolecular chain extender is 1: 4;
the properties of the silicone-polyurethane thermoplastic elastomer prepared are shown in table 1.
Example 6
Raw materials for preparing the silicone-polyurethane thermoplastic elastomer:
1) macromolecular silicone glycol:
wherein Q 1 And Q 2 is-CH 3 N is 20, X is-C 3 H 6 OC 2 H 4 -OH, shin & shin-Etsu chemical industries co., KF 6001;
2) a compatibilizer:
INDSPE Chemicals, TG-210;
3) diisocyanate: cyclohexane dimethylene diisocyanate, hexamethylene diisocyanate;
4) small-molecule chain extender: neopentyl glycol, 1, 4-butanediol;
i, mixing macromolecular organic silicon diol, a compatibilizer and diisocyanate according to a certain mode at the temperature of 100 ℃ to react to obtain an isocyanate-terminated prepolymer;
II, uniformly mixing the prepolymer obtained in the step I with a small molecular chain extender, pouring the mixture and curing to obtain the organic silicon-polyurethane thermoplastic elastomer;
the mixing mode in the step I is selected from a mode 3): firstly, uniformly mixing macromolecular organic silicon diol and a compatibilizer, and then gradually adding the mixture into diisocyanate;
in the raw materials for preparing the organic silicon-polyurethane thermoplastic elastomer, the mass fraction of macromolecular organic silicon diol is 62 wt%, the mass fraction of a compatibilizer is 8 wt%, the mass fraction of dicyanate is 20 wt%, and the mass fraction of a micromolecular chain extender is 10 wt%, based on the total amount of the raw materials. The molar ratio of isocyanic acid radical to active hydrogen in the raw material is 1, the mass ratio of cyclohexane dimethylene diisocyanate to hexamethylene diisocyanate in the diisocyanate is 1:2, and the mass ratio of neopentyl glycol to 1, 4-butanediol in the micromolecular chain extender is 1: 3;
the properties of the silicone-polyurethane thermoplastic elastomer prepared are shown in table 1.
Example 7
Raw materials for preparing the silicone-polyurethane thermoplastic elastomer:
1) macromolecular silicone glycol:
wherein Q 1 And Q 2 is-CH 3 N is 10 and X is-C 3 H 6 OC 2 H 4 -OH shin-Etsu chemical industry co., KF 6000;
2) a compatibilizer:
compatibilizer 1:
arch Corp., Poly-G;
compatibilizer 2:
SEPPIC corporation, france, Dianol 320;
3) diisocyanate: diphenylmethane diisocyanate;
4) small-molecule chain extender: 1, 6-hexanediol;
i, mixing macromolecular organic silicon diol, a compatibilizer and diisocyanate according to a certain mode at the temperature of 80 ℃ to react to obtain an isocyanate-terminated prepolymer;
II, uniformly mixing the prepolymer obtained in the step I with a small molecular chain extender, pouring the mixture and curing to obtain the organic silicon-polyurethane thermoplastic elastomer;
the mixing mode in the step I is selected from a mode 3): firstly, uniformly mixing macromolecular organic silicon diol and a compatibilizer, and then gradually adding the mixture into diisocyanate;
in the raw materials for preparing the organic silicon-polyurethane thermoplastic elastomer, the mass fraction of macromolecular organic silicon diol is 52 wt%, the mass fraction of a compatibilizer is 10 wt%, the mass fraction of dicyanate is 30 wt%, and the mass fraction of a micromolecular chain extender is 8 wt%, based on the total amount of the raw materials. The molar ratio of isocyanic acid radical to active hydrogen in the raw material is 1, and the mass ratio of a compatibilizer 1 to a compatibilizer 2 in the compatibilizer is 1: 2;
the properties of the silicone-polyurethane thermoplastic elastomer prepared are shown in table 1.
TABLE 1 Silicone-polyurethane thermoplastic elastomer Properties
By comparing comparative example 1 with the examples, it can be seen that: the mechanical properties of the examples are obviously improved compared with those of comparative example 1, particularly, the mechanical properties of example 4 can reach the grade of general TPU, and the prepared silicone-polyurethane thermoplastic elastomer also has excellent low-temperature resistance and hydrophobicity.
Claims (12)
1. A preparation method of a silicone-polyurethane thermoplastic elastomer is characterized by comprising the following steps:
i, mixing macromolecular organic silicon diol, a compatibilizer and diisocyanate according to a certain mode at the temperature of 50-120 ℃ to react to obtain an isocyanate-terminated prepolymer;
II, uniformly mixing the prepolymer obtained in the step I with a small molecular chain extender, pouring the mixture and curing to obtain the organic silicon-polyurethane thermoplastic elastomer;
the compatibilizer is at least one of the following molecular structures:
b 3 )
b 4 )
b 5 )
b 6 )
b 7 )
the mass fraction of macromolecular organic silicon diol in the raw materials for preparing the organic silicon-polyurethane thermoplastic elastomer is 42-69 wt%; the mass fraction of the compatibilizer is 1-15 wt%; the mass fraction of the diisocyanate is 10-40 wt%; the mass fraction of the micromolecule chain extender is 3-20 wt%; based on the total amount of the raw materials.
2. The method according to claim 1, wherein the mixing in step i is performed by any one of the following methods:
mode 1) sequentially adding macromolecular organic silicon diol and a compatibilizer into diisocyanate gradually;
mode 2) adding diisocyanate and compatibilizer gradually into macromolecular organic silicon diol;
mode 3) uniformly mixing macromolecular organic silicon diol and a compatibilizer, and gradually adding the mixture into diisocyanate;
mode 4) first uniformly mixing the macromolecular silicone glycol with the compatibilizer to obtain a mixture, and then gradually adding the diisocyanate to the mixture.
3. The method according to claim 2, wherein the mixing manner in step i is 3) that the macromolecular silicone diol and the compatibilizer are uniformly mixed and then the mixture is gradually added to the diisocyanate.
4. The method of any one of claims 1 to 3, wherein: the macromolecular organic silicon dihydric alcohol is hydroxyl-terminated polysiloxane and is any one of molecular structures shown in a structural formula I:
n in the structural formula I is an integer of 1-50, Q 1 And Q 2 is-CH 3 、
Any one of the above; x is the following a 1 ～a 9 Any one of the structures, a 1 )-C 3 H 6 -OH；a 2 )-C 4 H 8 -OH；a 3 )-C 5 H 10 -OH；a 4 )-C 6 H 12 -OH；a 5 )-C 3 H 6 OC 2 H 4 -OH；a 6 )-C 3 H 6 OCH 2 CH(OH)CH 2 OCH 3 ；
a 7 )
a 8 )
a 9 )
5. The method of manufacturing according to claim 4, characterized in that: in the structural formula I, n is an integer of 2-20, and X is a 1 、a 3 、a 5 Any one of the structures.
6. The method of any one of claims 1 to 3, wherein: the diisocyanate is at least one of aliphatic, alicyclic or aromatic diisocyanate.
7. The method of claim 6, wherein: the diisocyanate is at least one of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate, p-phenylene diisocyanate, naphthalene diisocyanate, 1, 4-cyclohexane diisocyanate, xylylene diisocyanate, cyclohexanedimethylene diisocyanate, trimethyl-1, 6-hexamethylene diisocyanate, tetramethyl m-xylylene diisocyanate, norbornane diisocyanate, dimethyl diphenyl diisocyanate, methylcyclohexyl diisocyanate, dimethyl diphenylmethane diisocyanate and lysine diisocyanate.
8. The method of any one of claims 1 to 3, wherein: the small molecular chain extender is one or more of ethylene glycol, 1, 4-butanediol, 1, 2-propanediol, neopentyl glycol, methyl propanediol, 1, 6-hexanediol, 1, 3-propanediol, butylethylpropanediol, diethylpentanediol, 3-methyl-1, 5-pentanediol, 1, 3-butanediol, 1, 2-butanediol, 2, 3-butanediol, trimethylpentanediol, 1, 5-pentanediol and 1, 2-pentanediol.
9. The method of claim 8, wherein: the micromolecule chain extender is one or more of ethylene glycol, 1, 4-butanediol, 1, 6-hexanediol, 1, 3-propanediol and 1, 5-pentanediol.
10. The method of claim 1, wherein: the mass fraction of macromolecular organic silicon diol in the raw materials for preparing the organic silicon-polyurethane thermoplastic elastomer is 50-60 wt%; the mass fraction of the compatibilizer is 5-10 wt%; the mass fraction of the diisocyanate is 20-30 wt%; the mass fraction of the micromolecule chain extender is 5-10 wt%; based on the total amount of the raw materials.
11. The method of any one of claims 1 to 3, wherein: the molar ratio of isocyanic acid radical to active hydrogen in the raw materials for preparing the organic silicon-polyurethane thermoplastic elastomer is 0.8-1.3.
12. The method of claim 11, wherein: the molar ratio of isocyanic acid radical to active hydrogen in the raw materials for preparing the organic silicon-polyurethane thermoplastic elastomer is 0.9-1.1.
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| CN109400842A (en) * | 2018-11-21 | 2019-03-01 | 广东中瀚新材料有限公司 | A kind of polyurethane elastomer material and its preparation method and application of width temperature range application |
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| CN110885550B (en) * | 2019-11-29 | 2021-09-17 | 东莞市吉鑫高分子科技有限公司 | Organic silicon modified thermoplastic polyurethane elastomer and preparation method thereof |
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| CN114634624B (en) * | 2020-12-16 | 2023-03-03 | 万华化学集团股份有限公司 | Polybutyronitrile organic silicon dihydric alcohol and preparation method thereof, transparent thermoplastic organic silicon polyurethane elastomer and application thereof |
| CN116041651B (en) * | 2022-12-15 | 2024-07-19 | 中国石油大学(北京) | An organic silicon polymer for thickening carbon dioxide, and its preparation method and application |
| CN116200025B (en) * | 2023-03-09 | 2025-02-11 | 山东大学 | A novel three-component blended polyurethane thermoplastic elastomer and its preparation method |
| CN120554646B (en) * | 2025-08-01 | 2025-10-03 | 湖北江特绝缘材料有限公司 | Structure-controllable polydimethylsiloxane poly ɛ -caprolactone block polymer dihydric alcohol and preparation method thereof |
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