CN114634623B - Macromolecular phosphorus-silicon dihydric alcohol and preparation method thereof, and fast-forming thermoplastic phosphorus-silicon polyurethane elastomer - Google Patents
Macromolecular phosphorus-silicon dihydric alcohol and preparation method thereof, and fast-forming thermoplastic phosphorus-silicon polyurethane elastomer Download PDFInfo
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Abstract
The invention provides macromolecular phosphorus-silicon dihydric alcohol and a preparation method thereof, and relates to a fast-forming thermoplastic phosphorus-silicon polyurethane elastomer. The macromolecular phosphorus-silicon dihydric alcohol has a structural formula as follows:
Description
Technical Field
The invention belongs to the fields of polyols and elastomer materials, and particularly relates to macromolecular phosphorus-silicon dihydric alcohol and a rapidly-formed thermoplastic phosphorus-silicon polyurethane elastomer.
Background
Thermoplastic Polyurethane (TPU) is a high-molecular synthetic material with excellent comprehensive performance, has excellent mechanical properties of high strength, high elasticity, high wear resistance and high flexibility, and also has oil resistance, solvent resistance and chemical resistance, and various TPU materials such as films, pipes, shoe materials, electric wires, cables, sheets and the like can be widely applied to various fields. Nevertheless, TPU is in the processing of moulding plastics, and its sclerosis shaping speed is not ideal enough always, especially to TPU's fast article of disappearing, like cell-phone sheath, watchband, intelligent bracelet etc. the rapid prototyping of goods can promote machining efficiency by a wide margin, and then reduce cost, increase benefit. Therefore, the preparation of a rapidly formed TPU is of great significance.
Patent CN103965614A discloses a preparation method of a rapidly molded thermoplastic polyurethane elastomer, namely a composite molecular lubricant composed of higher aliphatic alkane, higher aliphatic alcohol and alkyl ester lubricant is added in the synthetic reaction process of TPU, the prepared TPU has a faster molding hardening speed in injection molding processing, the molding time can be reduced from the traditional 45s to 35s, but the amplitude of the patent for improving the molding speed of an injection molded product is still not large enough.
The patent CN107141437A discloses a thermoplastic polyurethane material with controllable crystallization and a preparation method thereof, in the process of synthesizing the thermoplastic polyurethane material, the type and the dosage of a main chain extender and an auxiliary chain extender in a chain extender are controlled, and a cyclodextrin derivative is introduced at the same time, so that the control of the crystallization characteristic of the material is realized, and the molding speed of a product is controlled; patent CN107880531a discloses a thermoplastic polyurethane elastomer composite material, a preparation method and an application thereof, wherein a melt-processable and rapidly-formed composite material is obtained by adding a surface-treated layered and particulate filler into a semi-crystalline thermoplastic polyurethane elastomer. However, these patents do not quantitatively give the product how fast and slow it is formed.
The patent CN103865251A discloses a thermoplastic polyurethane elastomer injection molding composition and an injection molding product thereof, two or more TPU with different properties are blended to prepare a composition capable of effectively shortening the injection molding cycle; the patent CN1733817A adds PBT with high melting point into TPU, and the result shows that the existence of PBT with high melting point can effectively shorten the demoulding time of TPU, and the patent US5977268 adds modified terpene resin with low molecular weight and high softening point into TPU, and can effectively shorten the injection molding time of TPU. However, these patents have limited the application range because of the introduction of other polymers, which may cause changes in other properties of the modified TPU, such as mechanical strength, hardness, low temperature resistance, etc.
Although the prior art discloses fast forming TPUs and related processes, there are various problems and a need for a thermoplastic phospho-silicone polyurethane elastomer that can be formed fast and has otherwise excellent properties.
Disclosure of Invention
The invention aims to provide macromolecular phosphorus-silicon dihydric alcohol and a preparation method thereof, and provides a fast-forming thermoplastic phosphorus-silicon polyurethane elastomer (PSi-TPU). The PSi-TPU elastomer which not only has good mechanical and surface properties, but also especially has excellent molding and demolding properties is prepared by selecting macromolecular phosphorus-silicon dihydric alcohol with a special structure as one of raw materials and adopting a multi-step reaction method.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
a macromolecular phosphorus silicon dihydric alcohol has a structure shown in a formula (I):
wherein m is an integer from 1 to 20, preferably from 2 to 14, n is an integer from 1 to 10, preferably from 2 to 6, R 1 Is any one of alkyl and ether containing 1-6C, including but not limited to-CH 2 -、-CH 2 CH 2 CH 2 -、-CH 2 CH 2 OCH 2 -、-CH 2 CH 2 CH 2 OCH 2 CH 2 CH 2 -，R 2 Is any one of alkyl, ether and ester containing 1-8C, including but not limited to-CH 2 -、-CH 2 CH 2 CH 2 -、-CH 2 CH 2 OCH 2 CH 2 -、-CH 2 CH 2 CH 2 COOCH 2 CH 2 CH 2 CH 2 -。
The hydroxyl value of the macromolecular phosphorus-silicon glycol is 8-140mgKOH/g, preferably 16-112mgKOH/g; the acid value is 0.01 to 0.5mgKOH/g, preferably 0.01 to 0.3mgKOH/g.
The preparation method of the macromolecular phosphorus-silicon dihydric alcohol comprises the following steps: under the protection of inert gas, reacting organic phosphorus diacid (DOPO-COOH) and hydroxyl-terminated polydimethylsiloxane (PDMS-OH) for 2-5h at 150-230 ℃, then heating to 210-270 ℃ for reacting for 2-8h, then continuing to react under the vacuum condition until the hydroxyl value and the acid value are qualified, cooling and discharging to obtain the macromolecular phosphorus-silicon dihydric alcohol.
In the invention, the structures of DOPO-COOH and PDMS-OH are respectively shown as a formula (II) and a formula (III),
in the formulas (II) and (III), m is an integer of 1-20Preferably an integer from 2 to 14, R 1 Is any one of alkyl and ether containing 1-6C atoms, including but not limited to-CH 2 -、-CH 2 CH 2 CH 2 -、-CH 2 CH 2 OCH 2 -、-CH 2 CH 2 CH 2 OCH 2 CH 2 CH 2 -，R 2 Is any one of alkyl, ether and ester containing 1-8C, including but not limited to-CH 2 -、-CH 2 CH 2 CH 2 -、-CH 2 CH 2 OCH 2 CH 2 -、-CH 2 CH 2 CH 2 COOCH 2 CH 2 CH 2 CH 2 -。
In the preparation method of the macromolecular phosphorus-silicon dihydric alcohol, the molar ratio of PDMS-OH to DOPO-COOH is 1-2:1.
A fast-forming thermoplastic phosphorus-silicon polyurethane elastomer comprises the following raw materials in parts by weight of 100:
(1) Diisocyanate: 21 to 47 parts, preferably 26 to 38 parts;
(2) The macromolecular phosphorus-silicon dihydric alcohol of the invention: 4 to 32 parts, preferably 8 to 24 parts;
(3) Other macrodiols: 29 to 64 parts, preferably 37 to 56 parts;
(4) Small-molecule chain extender: 2 to 15 parts, preferably 5 to 10 parts.
In the present invention, the diisocyanate is one or more of aliphatic, alicyclic and aromatic diisocyanates, preferably 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, cyclohexane dimethylene diisocyanate, trimethyl-1,6-hexamethylene diisocyanate, tetramethyl-m-xylylene diisocyanate, norbornane diisocyanate, dimethylbiphenyl diisocyanate, methylcyclohexyl diisocyanate, dimethyldiphenylmethane diisocyanate, lysine diisocyanate; more preferably one or more of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate and p-phenylene diisocyanate.
In the invention, the molecular structure of the other macrodiol is HO-R 3 At least one of-OH and a number average molecular weight of 800 to 8000g/mol, preferably 1000 to 6000g/mol, wherein R 3 Has a structure of any one of aliphatic or aromatic polyester, polyether, polycarbonate, polylactic acid and polyolefin, preferably R 3 Is any one of aliphatic or aromatic polyester and polyether. Suitable examples include, but are not limited to, one or more of polytetrahydrofuran diol, polybutylene adipate diol, polycarbonate diol, poly (terephthalic acid) -1,6-hexanediol diol, polyoxypropylene diol, and the like.
In the invention, the micromolecule chain extender is one or more of aliphatic and/or aromatic micromolecule chain extenders, preference is given to ethylene glycol, 1,4-butanediol, diethylene glycol, triethylene glycol, 1,2-propanediol, neopentyl glycol, methylpropanediol, 1,6-hexanediol, 1,3-propanediol, dipropylene glycol, tripropylene glycol, butylethylpropanediol, diethylpentanediol, 3-methyl-1,5-pentanediol, 1,3-butanediol, 1,2-butanediol, 2,3-butanediol, trimethylpentanediol, 1,5-pentanediol, 1,2-pentanediol, hydroxypivalyl hydroxypivalate 2-ethyl-1,3-hexanediol, dodecanediol, 1,4-dimethylolcyclohexane, 1,4-cyclohexanediol, hydroquinone dihydroxyethyl ether, resorcinol dihydroxypropyl ether, 4-hydroxyethyloxyethyl-1-hydroxyethylphenylether, 3-hydroxyethyloxyethyl-1-hydroxyethylphenylether, bisphenol A dihydroxyethyl ether, bisphenol A dihydroxypropyl ether, 1,4-cyclohexanediamine, diaminodicyclohexylmethane, trimethylhexamethylenediamine, dimethyldiaminodicyclohexylmethane; more preferably one or more of ethylene glycol, 1,4-butanediol, diethylene glycol, 1,6-hexanediol, 1,3-propanediol, dipropylene glycol, 1,5-pentanediol, 1,4-cyclohexanediamine.
The preparation method of the thermoplastic phosphorus-silicon polyurethane elastomer comprises the following steps: according to the proportion,
1) Reacting diisocyanate with other macromolecular dihydric alcohol to obtain an NCO-terminated prepolymer I;
2) Reacting the prepolymer I with macromolecular phosphorus-silicon dihydric alcohol to obtain an NCO-terminated prepolymer II;
3) And reacting the micromolecular chain extender with the prepolymer II to obtain the thermoplastic phosphorus-silicon polyurethane elastomer.
In the invention, the reaction temperature of the step 1) is 60-140 ℃.
In the invention, the reaction temperature of the step 2) is 60-140 ℃.
In the invention, the reaction temperature of the step 3) is 60-160 ℃.
In the present invention, the NCO content of the prepolymer I obtained in step 1) is 5 to 13wt%, preferably 6 to 10wt%.
In the present invention, the NCO content of the prepolymer II in the step 2) is 2wt% to 8wt%, preferably 3wt% to 6wt%.
In the preparation method of the thermoplastic phosphorus-silicon polyurethane elastomer, the molar ratio of the total isocyanic acid radicals to the total active hydrogen in the used raw materials is 0.9-1.1.
According to the invention, the thermoplastic phosphorus-silicon polyurethane elastomer has excellent molding and demolding properties, can greatly shorten the injection molding period of a product, improves the processing efficiency, and further reduces the cost and increases the benefit.
The technical scheme provided by the invention has the following beneficial effects:
the invention selects diisocyanate, macromolecular phosphorus-silicon diol and the like as raw materials, and prepares a PSi-TPU elastomer through a multi-step reaction method, the elastomer material has good mechanical and surface properties, organic silicon and organic phosphorus in the structure can effectively form a synergistic effect, the material has excellent molding and demolding properties, the injection molding cycle of a product can be greatly shortened, the processing efficiency is improved, and further the cost is reduced and the benefit is increased.
Detailed Description
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.
Determination of the NCO content: the determination was carried out in accordance with Standard HGT2409-1992 "determination of the content of isocyanate groups in polyurethane prepolymers".
Example 1
The preparation method of the macromolecular phosphorus-silicon dihydric alcohol comprises the following steps:
adding DOPO-COOH
(R 1 is-CH 2 CH 2 -)、PDMS-OH
(R 2 is-CH 2 CH 2 CH 2 And m is 7), adding the mixture into a reaction kettle according to a molar ratio PDMS-OH/DOPO-COOH of 1.5. The hydroxyl value was 56mgKOH/g, and the acid value was 0.02mgKOH/g.
The raw materials for preparing the thermoplastic phosphorus-silicon polyurethane elastomer comprise, by weight, 100 parts:
(1) Diisocyanate: 33 parts of diphenylmethane diisocyanate;
(2) Macromolecular phosphorus silicon dihydric alcohol: 18 parts of a mixture;
(3) Other macrodiols: 42 parts of polytetrahydrofuran diol with the number average molecular weight of 2000 g/mol;
(4) Small-molecule chain extender: 1,4-butanediol, 7 parts.
The preparation method comprises the following steps:
1) Adding other macromolecular dihydric alcohol into diisocyanate at the temperature of 100 ℃, and obtaining an NCO-terminated prepolymer I after complete reaction, wherein the NCO content is 7.9wt%;
2) Adding macromolecular phosphorus-silicon dihydric alcohol into the prepolymer I at the same temperature as that in the step 1), and reacting completely to obtain an NCO-terminated prepolymer II, wherein the NCO content is 4.6wt%;
3) And fully mixing the micromolecule chain extender with the prepolymer II in the step 2) at the temperature of 80 ℃ and completely reacting to obtain the thermoplastic phosphorus-silicon polyurethane elastomer.
The molar ratio of the total isocyanate groups to the total active hydrogen in the raw materials is 1.02.
The properties of the thermoplastic phosphorus silicon polyurethane elastomer prepared are shown in table 1.
Comparative example 1
The raw materials for preparing the thermoplastic organic silicon polyurethane elastomer comprise, by weight, 100 parts:
(1) Diisocyanate: 33 parts of diphenylmethane diisocyanate;
(2) Macromolecular silicone glycol: 18 portions of formula
(m 1 Is 24);
(3) Other macrodiols: 42 parts of polytetrahydrofuran diol with the number average molecular weight of 2000 g/mol;
(4) Small-molecule chain extender: 1,4-butanediol, 7 parts.
The preparation method comprises the following steps:
1) Adding other macromolecular dihydric alcohol into diisocyanate at the temperature of 100 ℃, and obtaining an NCO-terminated prepolymer I after complete reaction, wherein the NCO content is 7.9wt%;
2) Adding macromolecular organic silicon dihydric alcohol into the prepolymer I at the same temperature as that in the step 1), and reacting completely to obtain an NCO-terminated prepolymer II, wherein the NCO content is 4.6wt%;
3) And fully mixing the micromolecular chain extender with the prepolymer II in the step 2) at the temperature of 80 ℃ and completely reacting to obtain the thermoplastic organic silicon polyurethane elastomer.
The molar ratio of the total isocyanate groups to the total active hydrogen in the raw materials is 1.02.
The properties of the thermoplastic silicone polyurethane elastomers prepared are shown in table 1.
Comparative example 2
The raw materials for preparing the thermoplastic polyurethane elastomer comprise, by weight, 100 parts:
(1) Diisocyanate: 33 parts of diphenylmethane diisocyanate;
(3) Other macrodiols: 60 parts of polytetrahydrofuran diol with the number average molecular weight of 2000 g/mol;
(4) Small-molecule chain extender: 1,4-butanediol, 7 parts.
The preparation method comprises the following steps:
1) Adding other macromolecular dihydric alcohol into diisocyanate at the temperature of 100 ℃, and obtaining an NCO-terminated prepolymer I after complete reaction, wherein the NCO content is 4.6wt%;
2) And fully mixing the micromolecular chain extender with the prepolymer I obtained in the step 2) at the temperature of 80 ℃ and completely reacting to obtain the thermoplastic polyurethane elastomer.
The molar ratio of the total isocyanate groups to the total active hydrogen in the raw materials for preparing the thermoplastic polyurethane elastomer is 1.02.
The properties of the thermoplastic polyurethane elastomer prepared are shown in table 1.
Example 2
The preparation method of the macromolecular phosphorus-silicon dihydric alcohol comprises the following steps:
DOPO-COOH
(R 1 is-CH 2 -)、PDMS-OH
(R 2 is-CH 2 CH 2 OCH 2 CH 2 CH 2 -, m is 14) at a molar ratio PDMS-OH/DOPO-COOH of 1.25:1 is added into a reaction kettle, under the protection of inert gas, the temperature of the system is increased to 180 ℃ for reaction for 5 hours, then the temperature is continuously increased to 230 ℃ for continuous reaction for 6 hours, then a vacuum system is started, the reaction is continuously carried out under the vacuum condition until the hydroxyl value and the acid value are qualified, and the macromolecule phosphorus-silicon dihydric alcohol is obtained after cooling and discharging. The hydroxyl value was 10mgKOH/g, and the acid value was 0.3mgKOH/g.
The raw materials for preparing the thermoplastic phosphorus-silicon polyurethane elastomer comprise, by weight, 100 parts:
(1) Diisocyanate: 26 parts of hexamethylene diisocyanate;
(2) Macromolecular phosphorus silicon dihydric alcohol: 8 parts of a mixture;
(3) Other macrodiols: 56 parts of polytetrahydrofuran diol with the number average molecular weight of 8000 g/mol;
(4) Small molecule chain extender: 1,6-hexanediol, 10 parts.
The preparation method comprises the following steps:
1) Adding other macromolecular dihydric alcohol into diisocyanate at the temperature of 140 ℃, and obtaining an NCO-terminated prepolymer I after complete reaction, wherein the NCO content is 6.0wt%;
2) Adding macromolecular phosphorus-silicon dihydric alcohol into the prepolymer I at the same temperature as that in the step 1), and reacting completely to obtain an NCO-terminated prepolymer II, wherein the NCO content is 3.3wt%;
3) And fully mixing the micromolecule chain extender with the prepolymer II in the step 2) at the temperature of 120 ℃ and completely reacting to obtain the thermoplastic phosphorus-silicon polyurethane elastomer.
The molar ratio of the total isocyanate groups to the total active hydrogen groups in the raw materials is 0.98.
The properties of the thermoplastic phosphorus silicon polyurethane elastomer prepared are shown in table 1.
Example 3
The preparation method of the macromolecular phosphorus-silicon dihydric alcohol comprises the following steps:
DOPO-COOH
(R 1 is-CH 2 CH 2 CH 2 -)、PDMS-OH
(m is 20, R) 2 is-CH 2 CH 2 CH 2 COOCH 2 CH 2 CH 2 CH 2 -) is added into a reaction kettle according to the molar ratio of PDMS-OH/DOPO-COOH of 1.75, the system is heated to 230 ℃ for reaction for 2 hours under the protection of inert gas, then the temperature is continuously raised to 270 ℃ for continuous reaction for 2 hours, then a vacuum system is started, the reaction is continued under the vacuum condition until the hydroxyl value and the acid value are qualified, and the macromolecule phosphorus-silicon dihydric alcohol is obtained after cooling and discharging. The hydroxyl value was 112mgKOH/g, and the acid value was 0.4mgKOH/g.
The raw materials for preparing the thermoplastic phosphorus-silicon polyurethane elastomer comprise, by weight, 100 parts:
(1) Diisocyanate: 47 parts of xylylene diisocyanate;
(2) Macromolecular phosphorus silicon dihydric alcohol: 19 parts of a mixture;
(3) Other macrodiols: 29 parts of polybutylene adipate diol with the number average molecular weight of 800 g/mol;
(4) Small-molecule chain extender: 1,4-butanediol, 5 parts.
The preparation method comprises the following steps:
1) Adding other macromolecular dihydric alcohol into diisocyanate at the temperature of 60 ℃, and obtaining an NCO-terminated prepolymer I after complete reaction, wherein the NCO content is 13.0wt%;
2) Adding macromolecular phosphorus-silicon dihydric alcohol into the prepolymer I at the same temperature as that in the step 1), and reacting completely to obtain an NCO-terminated prepolymer II, wherein the NCO content is 8.0wt%;
3) And fully mixing the micromolecule chain extender with the prepolymer II in the step 2) at the temperature of 60 ℃ and completely reacting to obtain the thermoplastic phosphorus-silicon polyurethane elastomer.
The molar ratio of the total isocyanate groups to the total active hydrogen in the raw materials is 1.1.
The properties of the thermoplastic phosphorus silicon polyurethane elastomer prepared are shown in table 1.
Example 4
The preparation method of the macromolecular phosphorus-silicon dihydric alcohol comprises the following steps:
adding DOPO-COOH
(R 1 is-CH 2 CH 2 CH 2 OCH 2 CH 2 CH 2 -)、PDMS-OH
(m is 1,R 2 is-CH 2 -) is added into a reaction kettle according to the molar ratio PDMS-OH/DOPO-COOH of 2:1, the system is heated to 160 ℃ to react for 5 hours under the protection of inert gas, then the temperature is continuously raised to 210 ℃ to continue to react for 4 hours, then a vacuum system is started, the reaction is continued under the vacuum condition until the hydroxyl value and the acid value are qualified, and the macromolecular phosphorosilicate dihydric alcohol is obtained after cooling and discharging. The hydroxyl value was 140mgKOH/g, and the acid value was 0.5mgKOH/g.
The raw materials for preparing the thermoplastic phosphorus-silicon polyurethane elastomer comprise, by weight, 100 parts:
(1) Diisocyanate: 21 parts of p-phenylene diisocyanate;
(2) Macromolecular phosphorus silicon dihydric alcohol: 13 parts;
(3) Other macrodiols: 64 parts of polyethylene glycol adipate with the number average molecular weight of 6000 g/mol;
(4) Small molecule chain extender: 2 portions of hydroquinone dihydroxyethyl ether.
The preparation method comprises the following steps:
1) Adding other macromolecular dihydric alcohol into diisocyanate at the temperature of 80 ℃, and obtaining an NCO-terminated prepolymer I after complete reaction, wherein the NCO content is 5.0wt%;
2) Adding macromolecular phosphorus-silicon dihydric alcohol into the prepolymer I at the same temperature as that in the step 1), and reacting completely to obtain an NCO-terminated prepolymer II, wherein the NCO content is 2.0wt%;
3) And fully mixing the micromolecule chain extender with the prepolymer II in the step 2) at the temperature of 90 ℃ and completely reacting to obtain the thermoplastic phosphorus-silicon polyurethane elastomer.
The molar ratio of the total isocyanate groups to the total active hydrogen in the raw materials is 0.9.
The properties of the thermoplastic phosphorus silicon polyurethane elastomer prepared are shown in table 1.
Example 5
The preparation method of the macromolecular phosphorus-silicon dihydric alcohol comprises the following steps:
adding DOPO-COOH
(R 1 is-CH 2 OCH 2 -)、PDMS-OH
(m is 2,R 2 is-CH 2 CH 2 -) is added into a reaction kettle according to the molar ratio of PDMS-OH/DOPO-COOH of 1.55, the system is heated to 150 ℃ for reaction for 3h under the protection of inert gas, then the temperature is continuously raised to 220 ℃ for continuous reaction for 4h, then a vacuum system is started, the reaction is continued under the vacuum condition until the hydroxyl value and the acid value are qualified, and the macromolecule phosphorus-silicon dihydric alcohol is obtained after cooling and discharging. The hydroxyl value was 121mgKOH/g, and the acid value was 0.18mgKOH/g.
The raw materials for preparing the thermoplastic phosphorus-silicon polyurethane elastomer comprise, by weight, 100 parts:
(1) Diisocyanate: 38 parts of isophorone diisocyanate;
(2) Macromolecular phosphorus silicon dihydric alcohol: 24 parts of (1);
(3) Other macrodiols: 30 parts of poly (terephthalic acid) -1,6-hexanediol ester with the number average molecular weight of 4000 g/mol;
(4) Small molecule chain extender: dipropylene glycol, 8 parts.
The preparation method comprises the following steps:
1) Adding other macromolecular dihydric alcohol into diisocyanate at the temperature of 90 ℃, and obtaining an NCO-terminated prepolymer I after complete reaction, wherein the NCO content is 10.0wt%;
2) Adding macromolecular phosphorus-silicon dihydric alcohol into the prepolymer I at the same temperature as that in the step 1), and reacting completely to obtain an NCO-terminated prepolymer II, wherein the NCO content is 6.0wt%;
3) And fully mixing the micromolecular chain extender with the prepolymer II in the step 2) at the temperature of 100 ℃ and completely reacting to obtain the thermoplastic phosphorus-silicon polyurethane elastomer.
The molar ratio of the total isocyanate groups to the total active hydrogen in the raw materials is 1.05.
The properties of the thermoplastic phosphorus silicon polyurethane elastomer prepared are shown in table 1.
Example 6
The preparation method of the macromolecular phosphorus-silicon dihydric alcohol comprises the following steps:
adding DOPO-COOH
(R 1 is-CH 2 CH 2 OCH 2 -)、PDMS-OH
(m is 6,R 2 is-CH 2 COOCH 2 CH 2 -) is added into a reaction kettle according to the molar ratio PDMS-OH/DOPO-COOH of 1.3. The hydroxyl value was 42mgKOH/g, and the acid value was 0.23mgKOH/g.
The raw materials for preparing the thermoplastic phosphorus-silicon polyurethane elastomer comprise, by weight, 100 parts:
(1) Diisocyanate: 24 parts of cyclohexane dimethylene diisocyanate;
(2) Macromolecular phosphorus silicon dihydric alcohol: 4 parts of a mixture;
(3) Other macrodiols: 57 parts of polycarbonate diol having a number average molecular weight of 7000 g/mol;
(4) Small-molecule chain extender: 1,4-cyclohexanediol, 15 parts.
The preparation method comprises the following steps:
1) Adding other macromolecular dihydric alcohol into diisocyanate at the temperature of 110 ℃, and obtaining an NCO-terminated prepolymer I after the reaction is completed, wherein the NCO content is 5.8wt%;
2) Adding macromolecular phosphorus-silicon dihydric alcohol into the prepolymer I at the same temperature as that in the step 1), and reacting completely to obtain an NCO-terminated prepolymer II, wherein the NCO content is 3.0wt%;
3) And fully mixing the micromolecule chain extender with the prepolymer II in the step 2) at the temperature of 160 ℃ and completely reacting to obtain the thermoplastic phosphorus-silicon polyurethane elastomer.
The molar ratio of the total isocyanate groups to the total active hydrogen groups in the raw materials is 1.01.
The properties of the thermoplastic phosphorus silicon polyurethane elastomer prepared are shown in table 1.
Example 7
The preparation method of the macromolecular phosphorus-silicon dihydric alcohol comprises the following steps:
DOPO-COOH
(R 1 is-CH 2 CH 2 -)、PDMS-OH
(m is 15, R) 2 is-CH 2 CH 2 OCH 2 CH 2 -) is added into a reaction kettle according to the molar ratio of PDMS-OH/DOPO-COOH of 1:1, the system is heated to 180 ℃ to react for 3 hours under the protection of inert gas, then the temperature is continuously raised to 240 ℃ to continue to react for 8 hours, then a vacuum system is started, the reaction is continued under the vacuum condition until the hydroxyl value and the acid value are qualified, and the macromolecule phosphorus-silicon dihydric alcohol is obtained after cooling and discharging. The hydroxyl value was 8mgKOH/g, and the acid value was 0.01mgKOH/g.
The raw materials for preparing the thermoplastic phosphorus-silicon polyurethane elastomer comprise, by weight, 100 parts:
(1) Diisocyanate: 27 parts of toluene diisocyanate;
(2) Macromolecular phosphorus silicon dihydric alcohol: 32 parts of (1);
(3) Other macrodiols: 37 parts of polyoxypropylene glycol having a number average molecular weight of 3000 g/mol;
(4) Small-molecule chain extender: 1,3-propylene glycol, 4 parts.
The preparation method comprises the following steps:
1) Adding other macromolecular dihydric alcohol into diisocyanate at the temperature of 120 ℃, and obtaining an NCO-terminated prepolymer I after complete reaction, wherein the NCO content is 6.7wt%;
2) Adding macromolecular phosphorus-silicon dihydric alcohol into the prepolymer I at the same temperature as that in the step 1), and reacting completely to obtain an NCO-terminated prepolymer II, wherein the NCO content is 2.8wt%;
3) And fully mixing the micromolecule chain extender with the prepolymer II in the step 2) at the temperature of 100 ℃ and completely reacting to obtain the thermoplastic phosphorus-silicon polyurethane elastomer.
The molar ratio of total isocyanate groups to total active hydrogen in the feed used was 1:1.
The properties of the thermoplastic phosphorus silicon polyurethane elastomer prepared are shown in table 1.
Example 8
The preparation method of the macromolecular phosphorus-silicon dihydric alcohol comprises the following steps:
adding DOPO-COOH
(R 1 is-CH 2 -)、PDMS-OH
(m is 8,R 2 is-CH 2 CH 2 CH 2 -) is added into a reaction kettle according to the molar ratio of PDMS-OH/DOPO-COOH of 1.2, the system is heated to 170 ℃ to react for 4h under the protection of inert gas, then the temperature is continuously raised to 260 ℃ to continue to react for 4h, then a vacuum system is started, the reaction is continued under the vacuum condition until the hydroxyl value and the acid value are qualified, and the macromolecule phosphorus-silicon dihydric alcohol is obtained after cooling and discharging. The hydroxyl value was 16mgKOH/g, and the acid value was 0.05mgKOH/g.
The raw materials for preparing the thermoplastic phosphorus-silicon polyurethane elastomer comprise, by weight, 100 parts:
(1) Diisocyanate: 35 parts of diphenylmethane diisocyanate;
(2) Macromolecular phosphorus silicon dihydric alcohol: 10 parts of (A);
(3) Other macrodiols: 48 parts of polytetrahydrofuran diol with the number average molecular weight of 3000 g/mol;
(4) Small-molecule chain extender: ethylene glycol, 7 parts.
The preparation method comprises the following steps:
1) Adding other macromolecular dihydric alcohol into diisocyanate at the temperature of 100 ℃, and obtaining an NCO-terminated prepolymer I after complete reaction, wherein the NCO content is 8.8wt%;
2) Adding macromolecular phosphorus-silicon dihydric alcohol into the prepolymer I at the same temperature as that in the step 1), and reacting completely to obtain an NCO-terminated prepolymer II, wherein the NCO content is 5.9wt%;
3) And fully mixing the micromolecule chain extender with the prepolymer II in the step 2) at the temperature of 90 ℃ and completely reacting to obtain the thermoplastic phosphorus-silicon polyurethane elastomer.
The molar ratio of the total isocyanate groups to the total active hydrogen groups in the raw materials is 1.01.
The properties of the thermoplastic phosphorus silicon polyurethane elastomer prepared are shown in table 1.
TABLE 1 thermoplastic phosphorus silicon polyurethane elastomer Properties
The conventional TPU is generally obtained by the reaction of macromolecular diol, a micromolecular chain extender and isocyanate, wherein the macromolecular diol forms a soft segment, the micromolecular chain extender and the isocyanate form a hard segment, the soft segment and the hard segment of the TPU are in a microphase separation state, and the forming and demolding performance of the TPU is mainly determined by the crystallization capacity of the hard segment and the soft segment, namely, the stronger the soft segment is aggregated into a phase, the stronger the crystallization capacity of the hard segment is, and the better the forming and demolding performance of the TPU is. When organic silicon and organic phosphorus with a special structure are combined to form macromolecular phosphorus-silicon dihydric alcohol, and the macromolecular phosphorus-silicon dihydric alcohol is used as a raw material to prepare the PSi-TPU elastomer, the organic silicon has extremely low solubility parameter and extremely poor compatibility, so that the soft-hard segment phase separation degree of the PSi-TPU is large, the hard segment Cheng Xiangjie crystal forming ability is strong, for the soft segment of the PSi-TPU, the soft segment phase separation degree is increased, and the special structure of the organic phosphorus is added, so that the aggregation phase forming ability of the soft segment is greatly improved, the PSi-TPU enhances the crystal forming ability of the soft-hard segment phase combination through the synergistic effect of the organic silicon and the organic phosphorus, and the forming and demolding performance is greatly improved.
Finally, it should be noted that the above-mentioned embodiments only illustrate the preferred embodiments of the present invention, and do not limit the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that various changes and modifications can be made by modifying the technical solution of the present invention or equivalent substitutions within the scope of the present invention defined by the claims.
Claims (14)
1. A macromolecular phosphorus silicon dihydric alcohol has a structural formula as follows:
wherein m is an integer of 1 to 20, n is an integer of 1 to 10, R 1 Is any one of alkyl and ether containing 1-6C, R 2 Is any one of alkyl, ether and ester containing 1-8C.
2. The macromolecular phospho-silicon diol according to claim 1, wherein m is an integer from 2 to 14, n is an integer from 2 to 6, and R is 1 is-CH 2 -、-CH 2 CH 2 CH 2 -、-CH 2 CH 2 OCH 2 -、-CH 2 CH 2 CH 2 OCH 2 CH 2 CH 2 -，R 2 is-CH 2 -、-CH 2 CH 2 CH 2 -、-CH 2 CH 2 OCH 2 CH 2 -、-CH 2 CH 2 CH 2 COOCH 2 CH 2 CH 2 CH 2 -。
3. The macromolecular phosphosilicate diol according to claim 1, wherein said macromolecular phosphosilicate diol has a hydroxyl value of 8-140mgKOH/g; the acid value is 0.01-0.5mgKOH/g.
4. The macromolecular phosphosilicate diol according to claim 1, wherein said macromolecular phosphosilicate diol has a hydroxyl value of 16-112mgKOH/g; the acid value is 0.01-0.3mgKOH/g.
5. A method for preparing a macromolecular phosphosilicate glycol according to any one of claims 1 to 4, comprising the steps of: under the protection of inert gas, reacting organic phosphorus diacid and hydroxyl-terminated polydimethylsiloxane at 150-230 ℃ for 2-5h, then heating to 210-270 ℃ for 2-8h, then continuing to react under the vacuum condition until the hydroxyl value and the acid value are qualified, cooling and discharging to obtain the macromolecular phosphorus-silicon dihydric alcohol.
6. The method of claim 5, wherein the organophosphorous diacid has the formula
The structural formula of the hydroxyl-terminated polydimethylsiloxane is shown as
Wherein m is an integer of 1 to 20, R 1 Is any one of alkyl and ether containing 1-6C, R 2 Is any one of alkyl, ether and ester containing 1-8C.
7. The method of claim 6, wherein m is an integer from 2 to 14, n is an integer from 2 to 6, and R is 1 is-CH 2 -、-CH 2 CH 2 CH 2 -、-CH 2 CH 2 OCH 2 -、-CH 2 CH 2 CH 2 OCH 2 CH 2 CH 2 -，R 2 is-CH 2 -、-CH 2 CH 2 CH 2 -、-CH 2 CH 2 OCH 2 CH 2 -、-CH 2 CH 2 CH 2 COOCH 2 CH 2 CH 2 CH 2 -。
8. The method of claim 5, wherein the hydroxyl terminated polydimethylsiloxane and the organophosphorous diacid are present in a molar ratio of from 1 to 2:1.
9. A fast-forming thermoplastic phosphorus-silicon polyurethane elastomer comprises the following raw materials in parts by weight of 100:
(1) Diisocyanate: 21-47 parts;
(2) The macromolecular phosphosilicate diol of any one of claims 1-4: 4-32 parts;
(3) Other macrodiols: 29-64 parts;
(4) Small-molecule chain extender: 2-15 parts;
the number average molecular weight of the other macrodiol is 800-8000 g/mol, and the other macrodiol is selected from one or more of polytetrahydrofuran diol, polybutylene adipate diol, polycarbonate diol, poly terephthalic acid-1,6-hexanediol diol and polypropylene oxide diol.
10. The thermoplastic phosphorus silicon polyurethane elastomer of claim 9, wherein the raw materials comprise the following components in 100 parts by weight:
(1) Diisocyanate: 26-38 parts;
(2) Macromolecular phosphorus silicon dihydric alcohol: 8-24 parts;
(3) Other macrodiols: 37-56 parts;
(4) Small-molecule chain extender: 5-10 parts;
the number average molecular weight of the other macromolecular dihydric alcohol is 1000-6000g/mol.
11. The thermoplastic phosphorus silicon polyurethane elastomer of claim 9, wherein the process for preparing the thermoplastic phosphorus silicon polyurethane elastomer comprises the steps of: according to the proportion of the components,
1) Reacting diisocyanate with other macromolecular dihydric alcohol to obtain an NCO-terminated prepolymer I;
2) Reacting the prepolymer I with macromolecular phosphorus-silicon dihydric alcohol to obtain an NCO-terminated prepolymer II;
3) And reacting the micromolecular chain extender with the prepolymer II to obtain the thermoplastic phosphorus-silicon polyurethane elastomer.
12. The thermoplastic phosphorus-silicon polyurethane elastomer according to claim 11, wherein the NCO content of prepolymer I obtained in step 1) is 5 to 13wt%; and/or, the NCO content of the prepolymer II in the step 2) is 2-8 wt%.
13. The thermoplastic phosphorus silicon polyurethane elastomer according to claim 11, wherein the NCO content of the prepolymer I obtained in step 1) is 6wt% to 10wt%; and/or, the NCO content of the prepolymer II in the step 2) is 3-6 wt%.
14. The thermoplastic phosphorus-silicon polyurethane elastomer according to claim 11, wherein the molar ratio of total isocyanate groups to total active hydrogen groups in the raw materials used is 0.9 to 1.1.
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| CN111154064A (en) * | 2020-01-03 | 2020-05-15 | 万华化学集团股份有限公司 | Fluorine-silicon type thermoplastic polyurethane elastomer and preparation method thereof |
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