CN104403070A - Preparation method for radiation-crosslinking modified polyurethane elastomer - Google Patents
Preparation method for radiation-crosslinking modified polyurethane elastomer Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
- C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
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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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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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
- 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
- C08G18/48—Polyethers
- C08G18/4866—Polyethers having a low unsaturation value
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/675—Low-molecular-weight compounds
- C08G18/679—Acetylenic compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/28—Treatment by wave energy or particle radiation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/14—Polyurethanes having carbon-to-carbon unsaturated bonds
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Abstract
The invention relates to a preparation method for a radiation-crosslinking modified polyurethane elastomer. The preparation method includes the following steps: 1) vacuum dewatering of mixed macromolecular polyether polyol is carried out at a temperature between 105 DEG C and 110 DEG C, 4,4'-diphenylmethane diisocyanate is then added after the temperature is reduced between 55 DEG C and 65 DEG C, the temperature is then slowly raised up to 80 plus or minus 2 DEG C, the reaction is carried out for 2.5 to 3 hours under nitrogen protection, and a polyurethane prepolymer is obtained after the temperature is reduced to the room temperature; 2) the polyurethane prepolymer is heated up to 80 plus or minus 2 DEG C, vacuum degassing is carried out for 1 to 2 hours, a chain extender is added, high-speed stirring and mixing are carried out for 2 to 3 minutes, the mixture is then poured into a preheated polytetrafluoroethylene mold, solidification is carried out for 24 to 48 hours at a temperature between 105 DEG C to 115 DEG C, curing is carried out for more than 7 days at the room temperature, and an elastomer sample needed is obtained; 3) the elastomer sample undergoes irradiation treatment through high-power electron beams at the room temperature, so as to obtain a product. The polyurethane elastomer achieves good dynamic property and high mechanical strength, that is, the dynamic endogenous heat is lower, and the mechanical strength is higher.
Description
Technical field
The invention belongs to extraordinary chemical material technical field, be specifically related to a kind of Irradiation Crosslinking Modification method for preparing polyurethane elastic body.
Background technology
In the hard section part of polyurethane elastomer, form hydrogen bond between hydrogen group (-NH-) and power supplying groups (=O), this physical crosslinking effect formed by hydrogen bond can promote orientation and the ordered arrangement of hard segment.But when being subject to larger dynamic repeated stress effect and higher temperature action, this hydrogen bond action is often easily broken gradually, thus making hard section crystalline region produce sliding rupture, making lag-effect serious, interior heat-dissipating becomes large.Chemical modification is carried out to hard section crystalline region, introduces chemically crosslinked structure in inside, hard section crystalline region, the destruction of hard section crystalline region under large sstrain and high-temperature can be effectively reduced, thus dynamic property raising is very helpful.
Radiation processing, in the preparation and modification work of macromolecular material, is mainly used in the fields such as radiation polymerization, irradiation grafting modification, irradiation-induced degradation and cross-linking radiation.Wherein radiation crosslinking can be used for the vulcanization of rubber, and some polyolefin based materials is cross-linking modified, can obtain good effect.The working method of radiation crosslinking is not high to conditional request, suitability for industrialized production facilitates feasible, treating processes is quick and easy, treatment effect is good, material can be made at additive-free impurity, being obtained by reacting desired product without carrying out under the condition of physical change, being therefore widely used in material modification research.Have report to carry out modification by the means of cross-linking radiation to Polyurethane Thermoplastic Elastomer (TPU), research finds the sample thermostability after radiation modification, and physical strength and stretching restorer all increase.And in casting type polyurethane elastomer (CPU), seldom have the research by radiation processing, it being carried out to aftertreatment.
Isosorbide-5-Nitrae-butynediol is a kind of chemical intermediate, mainly for the production of butyleneglycol and derived product thereof, also in electroplating industry, is used as brightening agent, because butynediol few people use it for the chainextender of polyurethane elastomer.Use 1,4-butynediol is as polyurethane elastomer chainextender, thus carbon carbon triple bond is introduced in hard segment molecule structure, make triple bond, in elastomerics inside, crosslinking reaction occur by the method for high-energy electron beam irradiation, form three-dimensional net structure, can obtain hard section " anchoring " the type polyurethane elastomerics of Irradiation Crosslinking Modification, this series products is all better than normal polyurethane elastomer in dynamic property and mechanical strength.
Summary of the invention
The object of this invention is to provide a kind of Irradiation Crosslinking Modification method for preparing polyurethane elastic body, polyurethane elastomer has good dynamic property and mechanical strength, has low dynamically interior heat-dissipating and the mechanical strength of Geng Gao.Suitability for industrialized production facilitates feasible, and radiation treatment polyvinyl chloride is simple, and treatment effect is good, makes material at additive-free impurity, is obtained by reacting desired product without carrying out under the condition of physical change.
Irradiation Crosslinking Modification method for preparing polyurethane elastic body of the present invention, the steps include:
1) mixing macromole polyether glycol is added in 1000ml there-necked flask, at 105-110 DEG C after vacuum hydro-extraction 2-2.5h, be cooled to 55-65 DEG C and add 4,4 '-diphenylmethanediisocyanate, slowly be warming up to 80 ± 2 DEG C again, react 2.5-3h under nitrogen protection, obtain urethane after being down to room temperature to performed polymer;
2) above-mentioned base polyurethane prepolymer for use as is heated to 80 ± 2 DEG C, vacuum outgas 1-2h, add the chainextender being preheated to 80 DEG C, pour in the Teflon mould of preheating after high-speed stirring mixing 2-3min, solidify 24-48h at 105-115 DEG C after, at room temperature post curing more than 7 days, obtains required elastomer sample;
3) elastomer sample is at room temperature used high-energy electron beam irradiation process, finally obtain Irradiation Crosslinking Modification polyurethane elastomer.
Described mixing macromole polyether glycol is one or more low-unsaturated polyether polyatomic alcohols of functionality 2-3, number-average molecular weight 1000-6000.One or more in preferred DL3000D, DL4000D, DL1000D or MN3050D, manufacturer is Shandong Lanxing Dongda Chemical Co., Ltd.
Described mixing macromole polyether glycol average functionality is 2-3, and mean number average molecular weight is one or more low-unsaturated polyether polyatomic alcohols of 2000-5000.
Described chainextender is Isosorbide-5-Nitrae-butynediol.
The NCO content of the base polyurethane prepolymer for use as described in step (1) is 5%-8%.
Chainextender more than vacuum hydro-extraction 90min at 100-110 DEG C in advance before adding reaction system.
Described high-energy electron beam irradiation beam intensity is 5-20mA.
Described high-energy electron beam irradiation dosage is 100-300kGy.
Compared with prior art, the present invention has following beneficial effect:
1, suitability for industrialized production of the present invention facilitates feasible, and radiation treatment polyvinyl chloride is simple, and treatment effect is good, makes material at additive-free impurity, is obtained by reacting desired product without carrying out under the condition of physical change;
2, the present invention is by selecting chainextender 1,4-butynediol introduces carbon carbon triple bond in the hard section of performed polymer, make triple bond, in elastomerics inside, crosslinking reaction occur by the method for high-energy electron beam irradiation, form three-dimensional net structure, thus make the polyurethane elastomer obtained have low dynamically interior heat-dissipating and the mechanical strength of Geng Gao.
Embodiment
The present invention is illustrated below in conjunction with embodiment.
Embodiment 1
(1) in 1000ml there-necked flask, add the Low unsaturation polyether DL3000D 600g that molecular weight is 3000; vacuum hydro-extraction 2h at 110 DEG C; be cooled to 60 DEG C; add and be heated to 4 of 75 DEG C and constant temperature in advance, 4 '-diphenylmethanediisocyanate (MDI) 220g, is slowly warming up to 80 DEG C; react 2.5h under nitrogen protection; sampling and testing-NCO content, reaches theoretical value 7% to performed polymer NCO content, obtains performed polymer after being down to room temperature.
(2) performed polymer that 150g obtains is got be heated to 80 DEG C, vacuum outgas 1h, add the chainextender 1 being preheated to 80 DEG C, 4-butynediol 10.13g, pour in the Teflon mould of preheating after high-speed stirring mixing 3min, solidify 24h at 110 DEG C after, at room temperature post curing 7 days, obtains required elastomer sample.
(3) elastomer sample is at room temperature used high-energy electron beam irradiation, beam intensity 10mA, irradiation dose 300kGy, finally obtain Irradiation Crosslinking Modification polyurethane elastomer.
Wherein, chainextender more than vacuum hydro-extraction 90min at 110 DEG C in advance before adding reaction system.
After testing, elastomer performance index lists in table 1.
Embodiment 2
The low-unsaturation-degree polyether trivalent alcohol MN3050D 300g that molecular weight is 3000 is added in 1000ml there-necked flask, molecular weight is the Low unsaturation polyether DL4000D 200g of 4000, molecular weight is the Low unsaturation polyether DL1000D 100g of 1000, vacuum hydro-extraction 2h at 110 DEG C, be cooled to 60 DEG C, add and be heated to 4 of 80 DEG C and constant temperature in advance, 4 '-diphenylmethanediisocyanate (MDI) 193g, slowly be warming up to 80 DEG C, react 2.5h under nitrogen protection, sampling and testing-NCO content, theoretical value 5% is reached to performed polymer NCO content, performed polymer is obtained after cooling.
The performed polymer obtained is got 150g and is heated to 80 DEG C, vacuum outgas 1h, add the chainextender 1 being preheated to 80 DEG C, 4-butynediol 7.23g, pour in the Teflon mould of preheating after high-speed stirring mixing 3min, solidify 24h at 110 DEG C after, at room temperature post curing 7 days, obtains required elastomer sample.
Elastomer sample is at room temperature used high-energy electron beam irradiation, beam intensity 30mA, irradiation dose 100kGy, finally obtain Irradiation Crosslinking Modification polyurethane elastomer.
Wherein, chainextender more than vacuum hydro-extraction 90min at 100 DEG C in advance before adding reaction system.
After testing, elastomer performance index lists in table 1.
Comparative example 1
Low unsaturation polyether (the preferred DL3000D that molecular weight is 3000 is added in 1000ml there-necked flask; blue star east is large) 600g; vacuum hydro-extraction 2h at 110 DEG C; be cooled to 60 DEG C; add and be heated to 4 of 70-80 DEG C and constant temperature in advance; 4 '-diphenylmethanediisocyanate (MDI) 220g; slowly be warming up to 80 DEG C; react 2.5h under nitrogen protection; sampling and testing-NCO content; reach theoretical value (7%) to performed polymer NCO content, after cooling, obtain performed polymer.The performed polymer obtained is got 150g and is heated to 80 DEG C, vacuum outgas 1h, add the chainextender 1 being preheated to 80 DEG C, 4-butyleneglycol 10.13g, pour in the Teflon mould of preheating after high-speed stirring mixing 3min, solidify 24h at 110 DEG C after, at room temperature post curing 7 days, obtains required elastomer sample.Elastomer sample is at room temperature used high-energy electron beam irradiation, beam intensity 10mA, irradiation dose 300kGy, finally obtain Irradiation Crosslinking Modification polyurethane elastomer.
After testing, elastomer performance index lists in table 1.
Comparative example 2
Low-unsaturation-degree polyether trivalent alcohol (the preferred MN3050D that molecular weight is 3000 is added in 1000ml there-necked flask, blue star east is large) 300g, molecular weight is Low unsaturation polyether (the preferred DL4000D of 4000, blue star east is large) 200g, molecular weight is Low unsaturation polyether (the preferred DL1000D of 1000, blue star east is large) 100g, vacuum hydro-extraction 2h at 110 DEG C, be cooled to 60 DEG C, add and be heated to 4 of 70-80 DEG C and constant temperature in advance, 4 '-diphenylmethanediisocyanate (MDI) 193g, slowly be warming up to 80 DEG C, react 2.5h under nitrogen protection, sampling and testing-NCO content, theoretical value (5%) is reached to performed polymer NCO content, performed polymer is obtained after cooling.The performed polymer obtained is got 150g and is heated to 80 DEG C, vacuum outgas 1h, add the chainextender 1 being preheated to 80 DEG C, 4-butyleneglycol 7.23g, pour in the Teflon mould of preheating after high-speed stirring mixing 3min, solidify 24h at 110 DEG C after, at room temperature post curing 7 days, obtains required elastomer sample.Elastomer sample is at room temperature used high-energy electron beam irradiation, beam intensity 30mA, irradiation dose 100kGy, finally obtain Irradiation Crosslinking Modification polyurethane elastomer.
After testing, elastomer performance index lists in table 1.
Table 1 executes routine 1-2, comparative example 1-2 fundamental property index
| Contrast project | Embodiment 1 | Comparative example 1 | Embodiment 2 | Comparative example 2 |
| Chainextender | Isosorbide-5-Nitrae-butynediol | BDO | Isosorbide-5-Nitrae-butynediol | BDO |
| Performed polymer NCO content/% | 7 | 7 | 5 | 5 |
| Beam intensity/mA | 10 | 10 | 30 | 30 |
| Irradiation dose/kGy | 300 | 300 | 100 | 100 |
| Dissipation factor tan δ (30 DEG C) | 0.056 | 0.067 | 0.054 | 0.066 |
| Dissipation factor tan δ (60 DEG C) | 0.032 | 0.054 | 0.034 | 0.056 |
| Tensile strength/MPa | 8.67 | 6.25 | 6.32 | 4.20 |
| 100% tensile modulus/MPa | 5.76 | 4.12 | 4.23 | 3.12 |
As seen from the above table: use 1,4-butynediol is chainextender, with directly use 1,4-butyleneglycol is the elastomerics contrast that chainextender obtains, under same NCO content, beam intensity and irradiation dose, modified sample dynamic loss factor in embodiment is all lower, and tensile strength and 100% tensile modulus are all higher than comparative example.As can be seen here, use chainextender 1,4-butynediol introduces carbon carbon triple bond in the hard section of performed polymer, make triple bond, in elastomerics inside, crosslinking reaction occur by the method for high-energy electron beam irradiation, form three-dimensional net structure, the polyurethane elastomer obtained can be made to have lower dynamically interior heat-dissipating and the mechanical strength of Geng Gao.
Claims (8)
1. an Irradiation Crosslinking Modification method for preparing polyurethane elastic body, is characterized in that: the steps include:
1) mixing macromole polyether glycol is added in 1000ml there-necked flask, at 105-110 DEG C after vacuum hydro-extraction 2-2.5h, be cooled to 55-65 DEG C and add 4,4 '-diphenylmethanediisocyanate, slowly be warming up to 80 ± 2 DEG C again, react 2.5-3h under nitrogen protection, obtain urethane after being down to room temperature to performed polymer;
2) above-mentioned base polyurethane prepolymer for use as is heated to 80 ± 2 DEG C, vacuum outgas 1-2h, add the chainextender being preheated to 80 DEG C, pour in the Teflon mould of preheating after high-speed stirring mixing 2-3min, solidify 24-48h at 105-115 DEG C after, at room temperature post curing more than 7 days, obtains required elastomer sample;
3) elastomer sample is at room temperature used high-energy electron beam irradiation process, finally obtain Irradiation Crosslinking Modification polyurethane elastomer.
2. a kind of Irradiation Crosslinking Modification method for preparing polyurethane elastic body according to claim 1, it is characterized in that: described mixing macromole polyether glycol is one or more low-unsaturated polyether polyatomic alcohols of functionality 2-3, number-average molecular weight 1000-6000.
3. a kind of Irradiation Crosslinking Modification method for preparing polyurethane elastic body according to claim 1 and 2, it is characterized in that: described mixing macromole polyether glycol average functionality is 2-3, and mean number average molecular weight is one or more low-unsaturated polyether polyatomic alcohols of 2000-5000.
4. a kind of Irradiation Crosslinking Modification method for preparing polyurethane elastic body according to claim 1, is characterized in that: described chainextender is Isosorbide-5-Nitrae-butynediol.
5. a kind of Irradiation Crosslinking Modification method for preparing polyurethane elastic body according to claim 1, is characterized in that: the NCO content of the base polyurethane prepolymer for use as described in step (1) is 5%-8%.
6. a kind of Irradiation Crosslinking Modification method for preparing polyurethane elastic body according to claim 1, is characterized in that: described chainextender more than vacuum hydro-extraction 90min at 100-110 DEG C in advance before adding reaction system.
7. a kind of Irradiation Crosslinking Modification method for preparing polyurethane elastic body according to claim 1, is characterized in that: described high-energy electron beam irradiation beam intensity is 5-20mA.
8. a kind of Irradiation Crosslinking Modification method for preparing polyurethane elastic body according to claim 1, is characterized in that: described high-energy electron beam irradiation dosage is 100-300kGy.
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Cited By (2)
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| CN108250383A (en) * | 2018-01-19 | 2018-07-06 | 盐城工学院 | More degree of cross linking polyurethane elastomers and preparation method thereof |
| CN108514436A (en) * | 2018-04-10 | 2018-09-11 | 段艳玲 | A kind of novel thyroid surgery drag hook |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108250383A (en) * | 2018-01-19 | 2018-07-06 | 盐城工学院 | More degree of cross linking polyurethane elastomers and preparation method thereof |
| CN108250383B (en) * | 2018-01-19 | 2020-09-08 | 盐城工学院 | Polyurethane elastomer with multiple crosslinking degrees and preparation method thereof |
| CN108514436A (en) * | 2018-04-10 | 2018-09-11 | 段艳玲 | A kind of novel thyroid surgery drag hook |
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Application publication date: 20150311 |