CN114805813A - Polysiloxane dihydric alcohol, thermoplastic organic silicon polyurethane elastomer, cross-linked polyurethane elastomer and application thereof - Google Patents
Polysiloxane dihydric alcohol, thermoplastic organic silicon polyurethane elastomer, cross-linked polyurethane elastomer and application thereof Download PDFInfo
- Publication number
- CN114805813A CN114805813A CN202110059972.8A CN202110059972A CN114805813A CN 114805813 A CN114805813 A CN 114805813A CN 202110059972 A CN202110059972 A CN 202110059972A CN 114805813 A CN114805813 A CN 114805813A
- Authority
- CN
- China
- Prior art keywords
- polyurethane elastomer
- parts
- diol
- thermoplastic
- diisocyanate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/28—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen sulfur-containing groups
-
- 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
- C08G18/61—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses polysiloxane dihydric alcohol, a thermoplastic organic silicon polyurethane elastomer, a cross-linked polyurethane elastomer and application thereof. The structural formula of the polysiloxane dihydric alcohol is shown in the specification
Description
Technical Field
The invention relates to the fields of polyols and elastomer materials, in particular to polysiloxane diol, a thermoplastic organic silicon polyurethane elastomer, a cross-linked polyurethane elastomer and application thereof.
Background
Thermoplastic polyurethane elastomer (TPU) is a comprehensive material composed of soft and hard segments which are not compatible with each other in thermodynamics and has excellent properties such as high strength, high toughness, high elasticity and the like, and the TPU can be prepared into diversified products such as pipes, films, complex molded bodies and the like by various melt processing methods such as injection molding, extrusion and the like, and can be widely applied to various industries.
For TPU articles such as seals, gaskets, wires and cables used in industry, conventional TPU products are difficult to meet because these articles are often subjected to environmental conditions such as chemicals, solvents, high temperatures, etc. which have stringent index requirements for their chemical resistance, dimensional stability, deformability, heat resistance, oxidation resistance, creep resistance, etc. It is known that thermoplastic resin materials differ from thermosetting resin materials mainly in that: most of linear polymers of thermoplastic resin materials can flow and deform after being heated, and can keep a certain shape after being cooled; the thermosetting resin material is in a network cross-linked structure, and cannot be plasticized again after being cured and molded, but the thermosetting resin has the characteristics of high temperature resistance, high rigidity, good product dimensional stability and the like due to chemical cross-linking, which is not possessed by the conventional thermoplastic resin material. Therefore, the crosslinkable thermoplastic polyurethane material is prepared, namely, the thermoplastic polyurethane is plastically processed into various products, and then the products are crosslinked by other technical methods to obtain the polyurethane product with a crosslinking structure, so that the polyurethane product can meet the requirements of the aforementioned severe indexes, and therefore, a plurality of scholars make related researches and provide corresponding solutions.
Patent CN102803331B prepared a crosslinkable thermoplastic polyurethane by introducing unsaturated carbon-carbon double bond units in the TPU backbone, which unsaturated units may be present in the soft segment or in the hard segment or in both the soft and hard segments of the TPU. The TPU may be molded like a thermoplastic and the unsaturated carbon-carbon double bond units may be subsequently crosslinked by means of electron beam radiation. Although the crosslinked TPU can be prepared by the patent, the crosslinking mode of electron beam radiation has the defects of high cost, complex equipment process, high operation difficulty and the like.
Patent CN110452354A provides a reversible crosslinking type thermoplastic polyurethane elastomer and a preparation method thereof, a mixture containing bismaleimide components and TPU increases the crosslinking effect among molecular chains through the reversible Diels-Alder (D-A) reaction of functional components, and the TPU has the thermoplastic property and is endowed with excellent self-repairing capability. Patent CN 101466755B prepared a crosslinkable thermoplastic polyurethane, which was a thermoset polyurethane with functionalized end groups at both ends that were free radically polymerizable, and obtained therefrom. However, the preparation methods of the patents have the disadvantages of multiple steps, complex process and high implementation difficulty.
Patent CN109517131A selects silicone diol as one of the raw materials to prepare a thermoplastic silicone polyurethane, but the used silicone raw material and other raw materials have no functional group capable of continuing reaction, so the thermoplastic silicone polyurethane cannot continue reaction to prepare the cross-linked silicone polyurethane elastomer.
Disclosure of Invention
The invention provides polysiloxane dihydric alcohol, a thermoplastic organic silicon polyurethane elastomer, a cross-linked polyurethane elastomer and application thereof. The thermal oxidation treatment method is simple in equipment and process, low in cost and remarkable in effect, and is used for carrying out thermal oxidation treatment on a thermoplastic organic silicon polyurethane elastomer (Si-TPU) matrix material containing-SiH and-SH groups in molecular chains, and under the specific thermal oxidation condition, the-SiH and-SH in the molecular chains of the Si-TPU can carry out cross-linking reaction to form cross-linking structures in molecules and among molecules of the Si-TPU matrix material, so that the cross-linked polyurethane elastomer material is prepared. Compared with Si-TPU base material, the prepared cross-linked polyurethane elastomer material has better comprehensive performance and can be applied to the material fields of sealing elements, gaskets, wires and cables and the like.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
a polysiloxane diol, which has a structure shown in formula (I):
wherein m is an integer of 6 to 24, preferably 10 to 18, and n 1 、n 2 Independently, the number of the groups is 4-16, preferably 6-12.
The preparation method of the polysiloxane diol comprises the following steps:
step I: adding 60-90 parts by weight of 2,4,6, 8-tetramethylcyclotetrasiloxane (CAS NO.2370-88-9), 10-40 parts by weight of end-capping agent deionized water, 20-60 parts by weight of isopropanol solvent and 0.02-0.5 part by weight of catalyst NaOH into a reaction kettle, heating to 50-80 ℃, reacting for 1-3 hours, adding phosphoric acid to neutralize the system to be neutral after the hydroxyl value is qualified, and removing the solvent to obtain the silicon hydroxyl end-capped hydrogen-containing silicone oil;
step II: adding 0.5-1.2 molar parts of 3-mercaptopropyl-methyldimethoxysilane (CAS NO.31001-77-1) and 1 molar part of the hydrogen-containing silicone oil with the silicon hydroxyl end capping prepared in the step I into a reaction kettle, adding hydrochloric acid, reacting for 2-4 hours at 60-90 ℃ with the concentration of the hydrochloric acid in the system being 1-3 wt%, adding 0.1-0.3 molar part of end capping agent tetrahydrofuran, reacting for 1-3 hours, washing with distilled water to be neutral after the hydroxyl value is qualified, and removing moisture to obtain the polysiloxane diol.
A thermoplastic organosilicon polyurethane elastomer is prepared from the following raw materials in parts by weight of 100 parts:
1) diisocyanate: 15-45 parts, preferably 25-38 parts;
2) the polysiloxane diols of the present invention: 2-40 parts, preferably 5-20 parts;
3) reactive macrodiol: 30-70 parts, preferably 40-60 parts;
4) small-molecule chain extender: 3 to 15 parts, preferably 5 to 12 parts.
In the present invention, the diisocyanate is at least one of aliphatic, alicyclic and aromatic diisocyanates, preferably one or more 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; more preferably one or more of toluene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane diisocyanate and p-phenylene diisocyanate.
In the invention, the reactive macrodiol adopts a molecular structure of HO-R 2 -OH and a number average molecular weight of 600 to 8000g/mol, preferably 1000 to 3000g/mol, wherein R 2 The structure of (a) is any one of aliphatic or aromatic polyester, polyether, polycarbonate, polycycloester, polylactic acid and polyolefin, preferably any one of aliphatic or aromatic polyester and polyether, more preferably any one of polytetrahydrofuran diol, polypropylene oxide diol, poly (1, 6-hexanediol terephthalate), poly (ethylene adipate) diol and poly (butylene adipate) diol.
In the invention, 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; preferably one or more of ethylene glycol, 1, 4-butanediol, 1, 6-hexanediol, 1, 3-propanediol and 1, 5-pentanediol.
The preparation method of the thermoplastic organic silicon polyurethane elastomer comprises the following steps: uniformly mixing polysiloxane diol, reactive macromolecular diol and a micromolecular chain extender according to a ratio to obtain a prepolymerization mixed solution, adding diisocyanate into the prepolymerization mixed solution at the temperature of 50-120 ℃, and carrying out reaction, pouring and curing.
A preparation method of a crosslinking polyurethane elastomer comprises the following steps: the thermoplastic silicone polyurethane elastomer of the present invention is subjected to thermal oxidation treatment.
The thermal oxidation treatment is to place the thermoplastic organic silicon polyurethane elastomer in oxygen-containing atmosphere for heating treatment, whereinThe oxygen-containing atmosphere being O 2 Mixtures with protective gases, O 2 Volume fraction V O2 Not less than 40%, preferably 50-70%, and the thermal oxidation treatment temperature is 110-200 ℃, preferably 130-180 ℃; the treatment time is 12-120 h, preferably 24-72 h.
In the present invention, the protective gas is helium (He), neon (Ne), argon (Ar), krypton (Kr), xenon (Xe), nitrogen (N) 2 ) Any one of argon (Ar) and nitrogen (N) is preferable 2 ) Any one of them.
In the invention, the crosslinking polyurethane elastomer can be applied to the fields of sealing elements, gaskets, wires and cables and other materials.
The positive progress effects of the invention are as follows:
1. different from the preparation principle of other crosslinking TPU, the invention prepares Si-TPU containing-SiH and-SH groups in a molecular chain, and takes the Si-TPU as a base material to prepare the crosslinking polyurethane elastomer material by utilizing the crosslinking reaction between-SiH and-SH under the special thermo-oxidative condition.
2. Compared with the existing energy beam radiation method for preparing the cross-linked material, the thermal oxidation treatment method adopted by the invention has the characteristics of simple equipment and process, low cost, obvious effect and the like;
3. compared with a Si-TPU base material, the prepared cross-linked polyurethane elastomer material has better comprehensive performance, particularly has obvious advantages in the aspects of mechanical property, chemical resistance, oxidation resistance, creep resistance and the like, and can be applied to the field with more severe environmental conditions.
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.
Example 1
The raw materials for preparing the thermoplastic organic silicon polyurethane elastomer comprise, by weight of 100 parts:
1) diisocyanate: 35 parts of diphenylmethane diisocyanate;
2) polysiloxane diol: 10 parts of a preparation method thereof, which comprises the following steps:
step I: adding 80 parts by weight of 2,4,6, 8-tetramethylcyclotetrasiloxane (CAS NO.2370-88-9), 20 parts by weight of end-capping agent deionized water, 40 parts by weight of isopropanol solvent and 0.2 part by weight of catalyst NaOH into a reaction kettle, heating to 70 ℃, reacting for 2 hours, sampling to determine that the hydroxyl value is 133mgKOH/g, adding phosphoric acid for neutralization until the system is neutral, and extracting the solvent under the condition of 100 ℃/-0.1MPa to obtain the silicon hydroxyl end-capped hydrogen-containing silicone oil;
step II: adding 0.8 molar part of 3-mercaptopropylmethyldimethoxysilane (CAS NO.31001-77-1) and 1 molar part of the silicon hydroxyl terminated hydrogen-containing silicone oil prepared in the step I into a reaction kettle, adding hydrochloric acid, wherein the concentration of the hydrochloric acid in the system is 2%, reacting for 3 hours at 70 ℃, adding 0.2 molar part of a capping agent tetrahydrofuran, reacting for 2 hours, sampling and determining that the hydroxyl value is 30mgKOH/g, washing with distilled water to be neutral, and removing the water of the system under the conditions of 80 ℃ and 0.1MPa to obtain the required polysiloxane diol;
3) reactive macrodiol: polytetrahydrofuran diol having a number average molecular weight of 2000 g/mol; 50 parts of a mixture;
4) small-molecule chain extender: ethylene glycol, 5 parts.
The process for preparing a thermoplastic silicone polyurethane elastomer comprises the steps of:
(1) uniformly mixing polysiloxane diol, reactive macromolecular diol and a micromolecular chain extender to obtain uniform prepolymerization mixed liquid, and (2) adding diisocyanate into the prepolymerization mixed liquid obtained in the step (1) at the temperature of 80 ℃, uniformly mixing, reacting, pouring and curing.
The method for preparing the cross-linked polyurethane elastomer material comprises the following steps:
placing the prepared thermoplastic organic silicon polyurethane elastomer in O at 150 DEG C 2 /N 2 ，V O2 Treating in 60% atmosphere for 36h to obtain cross-linkingA polyurethane elastomer material.
The properties of the prepared thermoplastic silicone polyurethane elastomer and the crosslinked polyurethane elastic material prepared therefrom are shown in table 1.
Comparative example 1
The raw materials for preparing the thermoplastic organic silicon polyurethane elastomer comprise, by weight of 100 parts:
1) diisocyanate: 35 parts of diphenylmethane diisocyanate;
2) polysiloxane diol: 10 parts of a preparation method thereof, which comprises the following steps: adding 4 molar parts of 3-mercaptopropylmethyldimethoxysilane (CAS NO.31001-77-1) into a reaction kettle, adding hydrochloric acid, wherein the concentration of the hydrochloric acid in the system is 2%, reacting for 3 hours at 70 ℃, adding 1 molar part of end-capping agent tetrahydrofuran, reacting for 2 hours, sampling and measuring the hydroxyl value to be 30mgKOH/g, washing to be neutral by using distilled water, and removing the water in the system under the condition of 80 ℃ to 0.1MPa to obtain the required polysiloxane diol;
3) reactive macrodiol: polytetrahydrofuran diol having a number average molecular weight of 2000 g/mol; 50 parts of a mixture;
4) small-molecule chain extender: ethylene glycol, 5 parts.
The process for preparing a thermoplastic silicone polyurethane elastomer comprises the steps of:
(1) uniformly mixing polysiloxane diol, reactive macromolecular diol and a micromolecular chain extender to obtain uniform prepolymerization mixed liquid, and (2) adding diisocyanate into the prepolymerization mixed liquid obtained in the step (1) at the temperature of 80 ℃, uniformly mixing, reacting, pouring and curing.
The method for preparing the cross-linked polyurethane elastomer material comprises the following steps:
placing the prepared thermoplastic organic silicon polyurethane elastomer in O at 150 DEG C 2 /N 2 ，V O2 Treating for 36h in 60% atmosphere to obtain the cross-linked polyurethane elastomer material.
The properties of the prepared thermoplastic silicone polyurethane elastomer and the crosslinked polyurethane elastic material prepared therefrom are shown in table 1.
Comparative example 2
The raw materials for preparing the thermoplastic organic silicon polyurethane elastomer comprise, by weight of 100 parts:
1) diisocyanate: 35 parts of diphenylmethane diisocyanate;
2) polysiloxane diol: 10 parts of a preparation method thereof, which comprises the following steps:
step I: adding 80 parts by weight of 2,4,6, 8-tetramethylcyclotetrasiloxane (CAS NO.2370-88-9), 20 parts by weight of end-capping agent deionized water, 40 parts by weight of isopropanol solvent and 0.2 part by weight of catalyst NaOH into a reaction kettle, heating to 70 ℃, reacting for 2 hours, sampling to determine that the hydroxyl value is 31mgKOH/g, adding phosphoric acid for neutralization until the system is neutral, and extracting the solvent under the conditions of 100 ℃/-0.1MPa to obtain the silicon hydroxyl end-capped hydrogen-containing silicone oil;
step II: adding 5 mol parts of the silicon hydroxyl terminated hydrogen-containing silicone oil prepared in the step I into a reaction kettle, adding hydrochloric acid, reacting for 3 hours at 70 ℃, adding 1 mol part of end-capping reagent tetrahydrofuran, reacting for 2 hours, sampling to determine that the hydroxyl value is 30mgKOH/g, washing to be neutral by using distilled water, and removing the water of the system under the condition of 80 ℃ minus 0.1MPa to obtain the needed polysiloxane diol;
3) reactive macrodiol: polytetrahydrofuran diol having a number average molecular weight of 2000 g/mol; 50 parts of a mixture;
4) small-molecule chain extender: ethylene glycol, 5 parts.
The process for preparing a thermoplastic silicone polyurethane elastomer comprises the steps of:
(1) uniformly mixing polysiloxane diol, reactive macromolecular diol and a micromolecular chain extender to obtain uniform prepolymerization mixed liquid, and (2) adding diisocyanate into the prepolymerization mixed liquid obtained in the step (1) at the temperature of 80 ℃, uniformly mixing, reacting, pouring and curing.
The method for preparing the cross-linked polyurethane elastomer material comprises the following steps:
placing the prepared thermoplastic organic silicon polyurethane elastomer in O at 150 DEG C 2 /N 2 ，V O2 Treating for 36h in 60% atmosphere to obtain the cross-linked polyurethane elastomer material.
The properties of the prepared thermoplastic silicone polyurethane elastomer and the crosslinked polyurethane elastic material prepared therefrom are shown in table 1.
Comparative example 3
The raw materials for preparing the thermoplastic polyurethane elastomer comprise, by weight of 100 parts:
1) diisocyanate: 35 parts of diphenylmethane diisocyanate;
2) reactive macrodiol: polytetrahydrofuran diol having a number average molecular weight of 2000 g/mol; 60 parts;
3) small-molecule chain extender: 5 parts of ethylene glycol;
the method for preparing the thermoplastic polyurethane elastomer comprises the following steps:
(1) uniformly mixing reactive macromolecular diol and a micromolecular chain extender to obtain uniform prepolymerization mixed liquid, and (2) adding diisocyanate into the prepolymerization mixed liquid obtained in the step (1) at the temperature of 80 ℃, uniformly mixing, reacting, pouring and curing.
The method for preparing the cross-linked polyurethane elastomer material comprises the following steps:
placing the prepared thermoplastic polyurethane elastomer in O at 150 DEG C 2 /N 2 ，V O2 Treating for 36h in 60% atmosphere to obtain the cross-linked polyurethane elastomer material.
The properties of the prepared thermoplastic polyurethane elastomer and the crosslinked polyurethane elastic material prepared therefrom are shown in table 1.
Example 2
The raw materials for preparing the thermoplastic organic silicon polyurethane elastomer comprise, by weight of 100 parts:
1) diisocyanate: 45 parts of hexamethylene diisocyanate;
2) polysiloxane diol: 5 parts of a preparation method of the composition, which comprises the following steps:
step I: adding 90 parts by weight of 2,4,6, 8-tetramethylcyclotetrasiloxane (CAS NO.2370-88-9), 10 parts by weight of end-capping agent deionized water, 20 parts by weight of isopropanol solvent and 0.4 part by weight of catalyst NaOH into a reaction kettle, heating to 60 ℃, reacting for 3 hours, sampling to determine that the hydroxyl value is 187mgKOH/g, adding phosphoric acid for neutralizing until the system is neutral, and extracting the solvent under the conditions of 100 ℃/-0.1MPa to obtain the silicon hydroxyl end-capped hydrogen-containing silicone oil;
step II: adding 0.6 molar part of 3-mercaptopropylmethyldimethoxysilane (CAS NO.31001-77-1) and 1 molar part of the hydrogen-containing silicone oil blocked by silicon hydroxyl prepared in the step I into a reaction kettle, adding hydrochloric acid, wherein the concentration of the hydrochloric acid in the system is 1%, reacting for 2 hours at 80 ℃, adding 0.3 molar part of blocking agent tetrahydrofuran, reacting for 2 hours, sampling, determining that the hydroxyl value is 61mgKOH/g, washing with distilled water to be neutral, and removing the water in the system under the conditions of 80 ℃ and 0.1MPa to obtain the needed polysiloxane diol;
3) reactive macrodiol: 1, 6-hexanediol poly (terephthalic acid), with a number average molecular weight of 600 g/mol; 47 parts of;
4) small-molecule chain extender: 3 portions of 1, 4-butanediol.
The process for preparing a thermoplastic silicone polyurethane elastomer comprises the steps of:
(1) uniformly mixing polysiloxane diol, reactive macromolecular diol and a micromolecular chain extender to obtain uniform prepolymerization mixed liquid, and (2) adding diisocyanate into the prepolymerization mixed liquid obtained in the step (1) at the temperature of 120 ℃, uniformly mixing, reacting, pouring and curing.
The method for preparing the cross-linked polyurethane elastomer material comprises the following steps:
placing the prepared thermoplastic organic silicon polyurethane elastomer in O at 180 DEG C 2 /He，V O2 And treating for 24 hours in 40% atmosphere to obtain the cross-linked polyurethane elastomer material.
The properties of the prepared thermoplastic silicone polyurethane elastomer and the crosslinked polyurethane elastic material prepared therefrom are shown in table 1.
Example 3
The raw materials for preparing the thermoplastic organic silicon polyurethane elastomer comprise, by weight of 100 parts:
1) diisocyanate: 25 parts of 1, 4-cyclohexane diisocyanate;
2) polysiloxane diol: 2 parts of a preparation method thereof, which comprises the following steps:
step I: adding 70 parts by weight of 2,4,6, 8-tetramethylcyclotetrasiloxane (CAS NO.2370-88-9), 30 parts by weight of end-capping agent deionized water, 30 parts by weight of isopropanol solvent and 0.5 part by weight of catalyst NaOH into a reaction kettle, heating to 80 ℃, reacting for 1 hour, sampling to determine that the hydroxyl value is 311mgKOH/g, adding phosphoric acid for neutralization until the system is neutral, and extracting the solvent under the conditions of 100 ℃/-0.1MPa to obtain the silicon hydroxyl end-capped hydrogen-containing silicone oil;
step II: adding 0.5 molar part of 3-mercaptopropylmethyldimethoxysilane (CAS NO.31001-77-1) and 1 molar part of the silicon hydroxyl terminated hydrogen-containing silicone oil prepared in the step I into a reaction kettle, adding hydrochloric acid, wherein the concentration of the hydrochloric acid in the system is 2%, reacting for 3 hours at 80 ℃, adding 0.1 molar part of a capping agent tetrahydrofuran, reacting for 1 hour, sampling and determining that the hydroxyl value is 53mgKOH/g, washing with distilled water to be neutral, and removing the water of the system under the conditions of 80 ℃ and 0.1MPa to obtain the required polysiloxane diol;
3) reactive macrodiol: polyethylene glycol adipate glycol with a number average molecular weight of 8000 g/mol; 70 parts of (B);
4) small-molecule chain extender: butyl ethyl propylene glycol, 3 parts.
The process for preparing a thermoplastic silicone polyurethane elastomer comprises the steps of:
(1) uniformly mixing polysiloxane diol, reactive macromolecular diol and a micromolecular chain extender to obtain uniform prepolymerization mixed liquid, and (2) adding diisocyanate into the prepolymerization mixed liquid obtained in the step I at the temperature of 100 ℃, uniformly mixing, reacting, pouring and curing.
The method for preparing the cross-linked polyurethane elastomer material comprises the following steps:
placing the prepared thermoplastic organic silicon polyurethane elastomer in O at 200 DEG C 2 /Ar，V O2 Treating in 50% atmosphere for 12h to obtain crosslinked polyurethane elastomerA bulk material.
The properties of the prepared thermoplastic silicone polyurethane elastomer and the crosslinked polyurethane elastic material prepared therefrom are shown in table 1.
Example 4
The raw materials for preparing the thermoplastic organic silicon polyurethane elastomer comprise, by weight of 100 parts:
1) diisocyanate: 38 parts of xylylene diisocyanate;
2) polysiloxane diol: 20 parts of a preparation method of the composition, which comprises the following steps:
step I: adding 60 parts by weight of 2,4,6, 8-tetramethylcyclotetrasiloxane (CAS NO.2370-88-9), 40 parts by weight of end-capping agent deionized water, 50 parts by weight of isopropanol solvent and 0.3 part by weight of catalyst NaOH into a reaction kettle, heating to 50 ℃, reacting for 2 hours, sampling to determine that the hydroxyl value is 104mgKOH/g, adding phosphoric acid for neutralization until the system is neutral, and extracting the solvent under the condition of 100 ℃/-0.1MPa to obtain the silicon hydroxyl end-capped hydrogen-containing silicone oil;
step II: adding 0.9 molar part of 3-mercaptopropylmethyldimethoxysilane (CAS NO.31001-77-1) and 1 molar part of the silicon hydroxyl terminated hydrogen-containing silicone oil prepared in the step I into a reaction kettle, adding hydrochloric acid, wherein the concentration of the hydrochloric acid in the system is 2%, reacting for 2 hours at 90 ℃, adding 0.3 molar part of a capping agent tetrahydrofuran, reacting for 2 hours, sampling and determining that the hydroxyl value is 22mgKOH/g, washing with distilled water to be neutral, and removing the water of the system under the conditions of 80 ℃ and 0.1MPa to obtain the required polysiloxane diol;
3) reactive macrodiol: polytetrahydrofuran diol, number average molecular weight 3000 g/mol; 35 parts of (B);
4) small-molecule chain extender: 7 parts of 1, 5-pentanediol.
The process for preparing a thermoplastic silicone polyurethane elastomer comprises the steps of:
(1) uniformly mixing polysiloxane diol, reactive macromolecular diol and a micromolecular chain extender to obtain uniform prepolymerization mixed liquid, and (2) adding diisocyanate into the prepolymerization mixed liquid obtained in the step I at the temperature of 90 ℃, uniformly mixing, reacting, pouring and curing.
The method for preparing the cross-linked polyurethane elastomer material comprises the following steps:
placing the prepared thermoplastic organic silicon polyurethane elastomer in O at 110 DEG C 2 /He，V O2 Treating for 120h in 70 percent atmosphere to obtain the cross-linked polyurethane elastomer material.
The properties of the prepared thermoplastic silicone polyurethane elastomer and the crosslinked polyurethane elastic material prepared therefrom are shown in table 1.
Example 5
The raw materials for preparing the thermoplastic organic silicon polyurethane elastomer comprise, by weight of 100 parts:
1) diisocyanate: 20 parts of diphenylmethane diisocyanate;
2) polysiloxane diol: 40 parts of the preparation method comprises the following steps:
step I: adding 80 parts by weight of 2,4,6, 8-tetramethylcyclotetrasiloxane (CAS NO.2370-88-9), 20 parts by weight of end-capping agent deionized water, 60 parts by weight of isopropanol solvent and 0.02 part by weight of catalyst NaOH into a reaction kettle, heating to 70 ℃, reacting for 2 hours, sampling to determine that the hydroxyl value is 233mgKOH/g, adding phosphoric acid for neutralization until the system is neutral, and extracting the solvent under the conditions of 100 ℃/-0.1MPa to obtain the silicon hydroxyl end-capped hydrogen-containing silicone oil;
step II: adding 1.2 molar parts of 3-mercaptopropylmethyldimethoxysilane (CAS NO.31001-77-1) and 1 molar part of the silicon hydroxyl terminated hydrogen-containing silicone oil prepared in the step I into a reaction kettle, adding hydrochloric acid, wherein the concentration of the hydrochloric acid in the system is 3%, reacting for 4 hours at 70 ℃, adding 0.1 molar part of a capping agent tetrahydrofuran, reacting for 3 hours, sampling and determining that the hydroxyl value is 23mgKOH/g, washing with distilled water to be neutral, and removing the water of the system under the conditions of 80 ℃ and 0.1MPa to obtain the required polysiloxane diol;
3) reactive macrodiol: polybutylene adipate glycol with the number average molecular weight of 4000 g/mol; 25 parts of (1);
4) small-molecule chain extender: 15 parts of 3-methyl-1, 5-pentanediol;
the process for preparing a thermoplastic silicone polyurethane elastomer comprises the steps of:
(1) uniformly mixing polysiloxane diol, reactive macromolecular diol and a micromolecular chain extender to obtain uniform prepolymerization mixed liquid, and (2) adding diisocyanate into the prepolymerization mixed liquid obtained in the step I at the temperature of 70 ℃, uniformly mixing, reacting, pouring and curing.
The method for preparing the cross-linked polyurethane elastomer material comprises the following steps:
placing the prepared thermoplastic organic silicon polyurethane elastomer in O at 120 DEG C 2 /N 2 ，V O2 And (3) treating for 96 hours in an atmosphere of 80% to obtain the cross-linked polyurethane elastomer material.
The properties of the prepared thermoplastic silicone polyurethane elastomer and the crosslinked polyurethane elastic material prepared therefrom are shown in table 1.
Example 6
The raw materials for preparing the thermoplastic organic silicon polyurethane elastomer comprise, by weight of 100 parts:
1) diisocyanate: 30 parts of diphenylmethane diisocyanate;
2) polysiloxane diol: 28 parts of a preparation method of the composition, which comprises the following steps:
step I: adding 90 parts by weight of 2,4,6, 8-tetramethylcyclotetrasiloxane (CAS NO.2370-88-9), 10 parts by weight of end-capping agent deionized water, 40 parts by weight of isopropanol solvent and 0.08 part by weight of catalyst NaOH into a reaction kettle, heating to 50 ℃, reacting for 3 hours, sampling to determine that the hydroxyl value is 78mgKOH/g, adding phosphoric acid for neutralization until the system is neutral, and extracting the solvent under the condition of 100 ℃/-0.1MPa to obtain the silicon hydroxyl end-capped hydrogen-containing silicone oil;
step II: adding 0.8 molar part of 3-mercaptopropylmethyldimethoxysilane (CAS NO.31001-77-1) and 1 molar part of the silicon hydroxyl terminated hydrogen-containing silicone oil prepared in the step I into a reaction kettle, adding hydrochloric acid, wherein the concentration of the hydrochloric acid in the system is 1%, reacting for 3 hours at 90 ℃, adding 0.3 molar part of a terminating agent tetrahydrofuran, reacting for 3 hours, sampling, determining that the hydroxyl value is 35mgKOH/g, washing with distilled water to be neutral, and removing the water of the system under the conditions of 80 ℃ and 0.1MPa to obtain the required polysiloxane diol;
3) reactive macrodiol: a polyoxypropylene diol having a number average molecular weight of 1000 g/mol; 30 parts of (1);
4) small-molecule chain extender: 1, 6-hexanediol, 12 parts.
The process for preparing a thermoplastic silicone polyurethane elastomer comprises the steps of:
i, uniformly mixing polysiloxane dihydric alcohol, reactive macromolecular dihydric alcohol and a micromolecular chain extender to obtain uniform prepolymerization mixed liquid, and II, adding diisocyanate into the prepolymerization mixed liquid obtained in the step I at the temperature of 50 ℃, uniformly mixing, reacting, pouring and curing.
The method for preparing the cross-linked polyurethane elastomer material comprises the following steps:
placing the prepared thermoplastic organic silicon polyurethane elastomer in O at 190 DEG C 2 /Ar，V O2 And treating for 72 hours in 45% atmosphere to obtain the cross-linked polyurethane elastomer material.
The properties of the prepared thermoplastic silicone polyurethane elastomer and the crosslinked polyurethane elastic material prepared therefrom are shown in table 1.
Example 7
The raw materials for preparing the thermoplastic organic silicon polyurethane elastomer comprise, by weight of 100 parts:
1) diisocyanate: 32 parts of hexamethylene diisocyanate;
2) polysiloxane diol: 12 parts of a preparation method thereof, which comprises the following steps:
step I: adding 60 parts by weight of 2,4,6, 8-tetramethylcyclotetrasiloxane (CAS NO.2370-88-9), 40 parts by weight of end-capping agent deionized water, 20 parts by weight of isopropanol solvent and 0.2 part by weight of catalyst NaOH into a reaction kettle, heating to 80 ℃, reacting for 1 hour, sampling to determine that the hydroxyl value is 85mgKOH/g, adding phosphoric acid for neutralization until the system is neutral, and extracting the solvent under the conditions of 100 ℃/-0.1MPa to obtain the silicon hydroxyl end-capped hydrogen-containing silicone oil;
step II: adding 1.1 molar part of 3-mercaptopropylmethyldimethoxysilane (CAS NO.31001-77-1) and 1 molar part of the silicon hydroxyl terminated hydrogen-containing silicone oil prepared in the step I into a reaction kettle, adding hydrochloric acid, wherein the concentration of the hydrochloric acid in the system is 2%, reacting for 4 hours at 80 ℃, adding 0.2 molar part of a capping agent tetrahydrofuran, reacting for 1 hour, sampling and determining that the hydroxyl value is 40mgKOH/g, washing with distilled water to be neutral, and removing the water of the system under the conditions of 80 ℃ and 0.1MPa to obtain the required polysiloxane diol;
3) reactive macrodiol: polytetrahydrofuran diol having a number average molecular weight of 2000 g/mol; 48 parts of a mixture;
4) small-molecule chain extender: ethylene glycol, 8 parts.
The process for preparing a thermoplastic silicone polyurethane elastomer comprises the steps of:
i, uniformly mixing polysiloxane dihydric alcohol, reactive macromolecular dihydric alcohol and a micromolecular chain extender to obtain uniform prepolymerization mixed liquid, and II, adding diisocyanate into the prepolymerization mixed liquid obtained in the step I at the temperature of 100 ℃, uniformly mixing, reacting, pouring and curing.
The method for preparing the cross-linked polyurethane elastomer material comprises the following steps:
placing the prepared thermoplastic organic silicon polyurethane elastomer in O at 130 DEG C 2 /N 2 ，V O2 And (3) treating for 18 hours in 75% atmosphere to obtain the cross-linked polyurethane elastomer material.
The properties of the prepared thermoplastic silicone polyurethane elastomer and the crosslinked polyurethane elastic material prepared therefrom are shown in table 1.
Example 8
The raw materials for preparing the thermoplastic organic silicon polyurethane elastomer comprise, by weight of 100 parts:
1) diisocyanate: 35 parts of diphenylmethane diisocyanate;
2) polysiloxane diol: 15 parts of a preparation method thereof, which comprises the following steps:
step I: adding 70 parts by weight of 2,4,6, 8-tetramethylcyclotetrasiloxane (CAS NO.2370-88-9), 30 parts by weight of end-capping agent deionized water, 30 parts by weight of isopropanol solvent and 0.15 part by weight of catalyst NaOH into a reaction kettle, heating to 60 ℃, reacting for 2 hours, sampling to determine that the hydroxyl value is 117mgKOH/g, adding phosphoric acid for neutralization until the system is neutral, and extracting the solvent under the condition of 100 ℃/-0.1MPa to obtain the silicon hydroxyl end-capped hydrogen-containing silicone oil;
step II: adding 0.7 molar part of 3-mercaptopropylmethyldimethoxysilane (CAS NO.31001-77-1) and 1 molar part of the hydrogen-containing silicone oil blocked by silicon hydroxyl prepared in the step I into a reaction kettle, adding hydrochloric acid, wherein the concentration of the hydrochloric acid in the system is 3%, reacting for 2 hours at 70 ℃, adding 0.3 molar part of blocking agent tetrahydrofuran, reacting for 3 hours, sampling, determining that the hydroxyl value is 29mgKOH/g, washing with distilled water to be neutral, and removing the water in the system under the condition of 80 ℃ and 0.1MPa to obtain the needed polysiloxane diol;
3) reactive macrodiol: polybutylene adipate diol, the number average molecular weight of which is 2000 g/mol; 45 parts of (1);
4) small-molecule chain extender: 5 parts of 1, 4-butanediol.
The process for preparing a thermoplastic silicone polyurethane elastomer comprises the steps of:
i, uniformly mixing polysiloxane dihydric alcohol, reactive macromolecular dihydric alcohol and a micromolecular chain extender to obtain uniform prepolymerization mixed liquid, and II, adding diisocyanate into the prepolymerization mixed liquid obtained in the step I at the temperature of 80 ℃, uniformly mixing, reacting, pouring and curing.
The method for preparing the cross-linked polyurethane elastomer material comprises the following steps:
placing the prepared thermoplastic organic silicon polyurethane elastomer in O at 160 DEG C 2 /N 2 ，V O2 Treating for 48 hours in an atmosphere of 50 percent to obtain the cross-linked polyurethane elastomer material.
The properties of the prepared thermoplastic silicone polyurethane elastomer and the crosslinked polyurethane elastic material prepared therefrom are shown in table 1.
TABLE 1 Properties of thermoplastic Silicone polyurethane Elastomers and crosslinked polyurethane elastomeric materials made therefrom
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 (9)
1. A polysiloxane diol with the structural formula
Wherein m is an integer of 6 to 24, preferably 10 to 18, and n 1 、n 2 Independently, the number of the groups is 4-16, preferably 6-12.
2. A method of making the polysiloxane diol of claim 1, comprising the steps of: adding 0.5-1.2 molar parts of 3-mercaptopropyl-methyldimethoxysilane and 1 molar part of silicon hydroxyl terminated hydrogen-containing silicone oil into a reaction kettle, adding hydrochloric acid, wherein the concentration of the hydrochloric acid in the system is 1-3 wt%, reacting for 2-4 hours at 60-90 ℃, adding 0.1-0.3 molar part of end capping agent tetrahydrofuran, reacting for 1-3 hours, washing with distilled water to be neutral after the hydroxyl value is qualified, and removing moisture to obtain the polysiloxane diol.
3. A thermoplastic organosilicon polyurethane elastomer is prepared from the following raw materials in parts by weight of 100 parts:
1) diisocyanate: 15-45 parts, preferably 25-38 parts;
2) the silicone glycol of claim 1: 2-40 parts, preferably 5-20 parts;
3) reactive macrodiol: 30-70 parts, preferably 40-60 parts;
4) small-molecule chain extender: 3 to 15 parts, preferably 5 to 12 parts.
4. The thermoplastic silicone polyurethane elastomer of claim 3, wherein the reactive macrodiol has a number average molecular weight of 600 to 8000g/mol, preferably 1000 to 3000g/mol, preferably one or more of polytetrahydrofuran diol, polyoxypropylene diol, poly (1, 6-hexanediol terephthalate), poly (ethylene adipate) diol, and poly (butylene adipate) diol.
5. The thermoplastic silicone polyurethane elastomer of claim 3, wherein the small molecule 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, butyl ethyl propanediol, diethyl pentanediol, 3-methyl-1, 5-pentanediol, 1, 3-butanediol, 1, 2-butanediol, 2, 3-butanediol, trimethyl pentanediol, 1, 5-pentanediol, 1, 2-pentanediol.
6. The thermoplastic silicone polyurethane elastomer of any one of claims 3-5, wherein the process for preparing comprises the steps of: uniformly mixing polysiloxane diol, reactive macromolecular diol and a micromolecular chain extender according to a ratio to obtain a prepolymerization mixed solution, adding diisocyanate into the prepolymerization mixed solution at the temperature of 50-120 ℃, and carrying out reaction, pouring and curing.
7. A crosslinked polyurethane elastomer, wherein the thermoplastic silicone polyurethane elastomer according to any one of claims 3 to 6 is subjected to a thermal oxidation treatment.
8. The crosslinked polyurethane elastomer of claim 7, wherein the thermal oxygen treatment is placing the thermoplastic silicone polyurethane elastomer in an oxygen-containing atmosphereHeat treatment in which the oxygen-containing atmosphere is O 2 Mixtures with protective gases, O 2 Volume fraction V O2 Not less than 40%, preferably 50-70%, and the thermal oxidation treatment temperature is 110-200 ℃, preferably 130-180 ℃; the treatment time is 12-120 h, preferably 24-72 h.
9. Use of the cross-linked polyurethane elastomer according to claim 7 or 8 for seals, gaskets, wires and cables.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110059972.8A CN114805813B (en) | 2021-01-18 | 2021-01-18 | Polysiloxane dihydric alcohol, thermoplastic organic silicon polyurethane elastomer, cross-linked polyurethane elastomer and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110059972.8A CN114805813B (en) | 2021-01-18 | 2021-01-18 | Polysiloxane dihydric alcohol, thermoplastic organic silicon polyurethane elastomer, cross-linked polyurethane elastomer and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114805813A true CN114805813A (en) | 2022-07-29 |
| CN114805813B CN114805813B (en) | 2023-03-28 |
Family
ID=82525020
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110059972.8A Active CN114805813B (en) | 2021-01-18 | 2021-01-18 | Polysiloxane dihydric alcohol, thermoplastic organic silicon polyurethane elastomer, cross-linked polyurethane elastomer and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114805813B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112979962A (en) * | 2021-02-04 | 2021-06-18 | 成都思立可科技有限公司 | Branched-chain type organic silicon modified polyurethane elastomer and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4234697A (en) * | 1979-01-18 | 1980-11-18 | Dow Corning Corporation | Method of preparing cross-linked polydiorganosiloxane using organic isocyanates and products prepared therefrom |
| CN102414240A (en) * | 2009-04-30 | 2012-04-11 | 道康宁东丽株式会社 | Polyurethane and manufacturing method therefor, master batch, ink binder, ink composition, thermoplastic polymer composition for molding, molded body, and compound molded body and manufacturing method therefor |
| CN103980450A (en) * | 2014-06-10 | 2014-08-13 | 山东省农业科学院农业质量标准与检测技术研究所 | Method for preparing organosilicon modified cationic waterborne polyurethane |
| CN106398215A (en) * | 2016-08-19 | 2017-02-15 | 青岛科技大学 | Preparation method of flexible polysiloxane electronic packaging material |
| CN106716182A (en) * | 2014-09-26 | 2017-05-24 | 诺华股份有限公司 | Polymerizable polysiloxanes with hydrophilic substituents |
| CN108610635A (en) * | 2018-05-08 | 2018-10-02 | 山东大学 | A kind of organic luminescence from silicon method for producing elastomers |
| CN109485826A (en) * | 2018-11-12 | 2019-03-19 | 万华化学集团股份有限公司 | A kind of branched chain type thermoplastic silicone polyurethane elastomer and preparation method thereof |
-
2021
- 2021-01-18 CN CN202110059972.8A patent/CN114805813B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4234697A (en) * | 1979-01-18 | 1980-11-18 | Dow Corning Corporation | Method of preparing cross-linked polydiorganosiloxane using organic isocyanates and products prepared therefrom |
| CN102414240A (en) * | 2009-04-30 | 2012-04-11 | 道康宁东丽株式会社 | Polyurethane and manufacturing method therefor, master batch, ink binder, ink composition, thermoplastic polymer composition for molding, molded body, and compound molded body and manufacturing method therefor |
| CN103980450A (en) * | 2014-06-10 | 2014-08-13 | 山东省农业科学院农业质量标准与检测技术研究所 | Method for preparing organosilicon modified cationic waterborne polyurethane |
| CN106716182A (en) * | 2014-09-26 | 2017-05-24 | 诺华股份有限公司 | Polymerizable polysiloxanes with hydrophilic substituents |
| CN106398215A (en) * | 2016-08-19 | 2017-02-15 | 青岛科技大学 | Preparation method of flexible polysiloxane electronic packaging material |
| CN108610635A (en) * | 2018-05-08 | 2018-10-02 | 山东大学 | A kind of organic luminescence from silicon method for producing elastomers |
| CN109485826A (en) * | 2018-11-12 | 2019-03-19 | 万华化学集团股份有限公司 | A kind of branched chain type thermoplastic silicone polyurethane elastomer and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112979962A (en) * | 2021-02-04 | 2021-06-18 | 成都思立可科技有限公司 | Branched-chain type organic silicon modified polyurethane elastomer and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114805813B (en) | 2023-03-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104448197B (en) | The synthetic method of the Heat-resistant Polyurethane Elastomers | |
| CN111234175B (en) | Preparation method of self-repairing waterproof material, self-repairing waterproof material and application of self-repairing waterproof material | |
| CN113105607B (en) | Self-repairing polyurethane cross-linked network containing UPy side chain, preparation method and application | |
| EP0299068B1 (en) | Process for producing polyurethane | |
| CN110452354B (en) | Reversible crosslinking type thermoplastic polyurethane elastomer and preparation method thereof | |
| CN112239530A (en) | Novel method for preparing hydrophobic self-healing super-elastic polyurethane elastomer | |
| CN114805813B (en) | Polysiloxane dihydric alcohol, thermoplastic organic silicon polyurethane elastomer, cross-linked polyurethane elastomer and application thereof | |
| US5288842A (en) | Morphological composite materials formed from different precursors | |
| CN112225872A (en) | Waterborne polyurethane and preparation method thereof | |
| CN113896854B (en) | Castor oil-based shape memory polymer and preparation method thereof | |
| EP0572682A1 (en) | Process for producing high-molecular aliphatic polyester, and film | |
| CN115536803B (en) | Preparation method of sulfur dioxide-based polysulfate polyurethane | |
| KR101601782B1 (en) | Fiber reinforced tpu composites | |
| CN111040419B (en) | Bio-based polyester type polyurethane film and preparation method thereof | |
| CN110845838A (en) | Polycarbonate type polyurethane film and preparation thereof | |
| JPS63286431A (en) | Polyamide-imide elastomer and production thereof | |
| TWI667266B (en) | Use of polymerizable ultraviolet absorber in polyurethane and composition for forming polyurethane comprising the same | |
| CN114835878A (en) | Low-temperature-resistant high-resilience polyurethane elastomer and preparation method thereof | |
| CN109929084B (en) | Novel polyether ester elastomer and preparation method thereof | |
| CN112661928A (en) | Novel polyurethane packaging material film and preparation thereof | |
| CN113527625B (en) | Polyurethane elastomer preform and method for producing polyurethane elastomer | |
| KR20200136237A (en) | Manufacturing method of polyurethane resin for coating fabric using biomass contents | |
| CN114057971B (en) | Thermoplastic polyurethane elastomer and preparation method thereof | |
| JPH0769016B2 (en) | Urethane packing | |
| CN109467666A (en) | A kind of preparation method of the polyurethane of surface slip |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |