CN102250310A - Polyurethane resin composite as well as preparation method and application thereof - Google Patents
Polyurethane resin composite as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a polyurethane resin composite as well as a preparation method and application thereof. The polyurethane resin composite comprises a component A and a component B, wherein the component A includes the following materials in parts by mass: 100 parts of hydroxy-terminated polybutadiene or hydrogenated hydroxy-terminated polybutadiene, 10-60 parts of plasticiser and 15-30 parts of isocyanate; the component B includes the following materials in parts by mass: 7-20 parts of organic amine hardener, 0-5 parts of light stabilizer, 0-2 parts of flatting agent and 0.1-0.5 part of foam suppressor; and the mass ratio of the component A to the component B is 100: (6-10). The obtained polyurethane material has the advantages of low shrinkage rate and better mechanical property and processing property and can be used for filling between shear cams of ballastless tracks of a high-speed railway and semicircular notches of track slabs.
Description
Technical field
The present invention relates to a kind of polyurethane resin composition and its production and use, particularly the Polyurethane Filling Resin in Aqueous of high-speed railway Line for Passenger Transportation non-fragment orbit use.
Background technology
Conventional railway is on the basis of fritter stone (tiny fragments of stone, coal, etc.), re-lays sleeper or cement rail, and this railroad train speed is restricted, and is unsuitable for train and runs at high speed.Non-fragment orbit also claims the novel track structure, train travel speed in the above is faster, more steady, it is more comfortable that the passenger feels, can reduce simultaneously maintenance, reduce dust, beautify the environment, and train speed per hour can reach more than 200 kilometers, is the trend and direction of the development of world's railway construction at present and in the future.
The structure formation of the non-fragment orbit that the high-speed railway Line for Passenger Transportation uses is more, and domestic using always is pillow formula and board-like.Track template formula size should consider that track is stressed evenly, the operability when taking into account manufacturing, loading transportation and construction again.Convex blocking platform is the stop means of slab track, directly bears the longitudinal force and the transverse force of circuit.Adopt around the convex blocking platform good springiness, resin material that intensity is high to substitute CA mortar (generally adopting cement, emulsified bitumen, sand and various Additive to mix, common name CA mortar).The design thickness of potting resin is 40mm between convex blocking platform and track plate half round cut.Boss resin dosing equipment view is seen Figure of description 1 and 2.
The low price resin filling materials that is suitable for site operation mainly contains: Resins, epoxy, unsaturated polyester resin, liquid macroimolecule urethane resin.
Epoxy resin at room temp solidifies slow, and the elasticity adjustable range is little, and intensity is good, and is hard and crisp, poor flexibility.
Unsaturated polyester resin, self-vulcanizing is fast, and viscosity is low, and is hard and crisp.
Curable urethane resin speed is very fast, and the elasticity adjustment is easy and adjustable range is big, and intensity is placed in the middle, but room temperature construction self-vulcanizing.
CN101037536A adopts polyurethane composition to prepare the packing material of ballastless track convex retaining platform, and the polyol component of its use is mainly the polyoxypropyleneglycol polyethers, and the product shrinking percentage of preparation is big, all 1.2%～2.8%.
The provisional technical qualification of Line for Passenger Transportation CRTS I template formula ballastless track convex retaining platform filled polyurethane resin (CPU) ((2008) No. 74 files of science and technology base), author: the Ministry of Railways, press: China Railway Press, date of publication: 200806, book number 151132776, appendix B in the literary composition (standardization appendix) has provided the cure shrinkage test method.Testing sequence: in the 1000mm glass test tube, inject 900mm boss resin mixture liquor, park 24h, adopt the vernier caliper measurement shrinkage of resin in vitro, accurately to 0.02mm.The arithmetic mean value of getting 3 tests is as test-results.Performance index require cure shrinkage≤10mm.
Summary of the invention
First technical problem that the present invention will solve provides a kind of polyurethane resin composition, and it is little that said composition is solidified post-shrinkage ratio.
Second technical problem that the present invention will solve provides a kind of preparation method of said composition.
The 3rd technical problem that the present invention will solve provides a kind of purposes of said composition.
The present invention is directed to the existing big deficiency of urethane resin shrinking percentage, a kind of improved polyurethane composition is provided.Technical scheme of the present invention is: be main raw material with hydroxy-terminated polybutadienes or hydrogenation hydroxy-terminated polybutadienes in the polyurethane composition, and by in urethane resin, adding softening agent cheap and easy to get, make the gained polyurethane material have low shrinking percentage, have mechanical property and processing performance preferably simultaneously, reduced cost again.
Polyurethane resin composition of the present invention comprises A, B two components, comprises following composition by mass parts:
(1) A component: 100 parts of hydroxy-terminated polybutadienes or hydrogenation hydroxy-terminated polybutadieness, 10～60 parts in softening agent, 15～30 parts of isocyanic ester.
(2) B component: 7～20 parts of organic amine curing agent, 0～5 part of photostabilizer, 0～2 part of flow agent, 0.1～0.5 part of defoamer.
The mass ratio of A, B component is 100: 6～10.
The molecular weight 1500～4000 of hydroxy-terminated polybutadienes or hydrogenation hydroxy-terminated polybutadienes is better.
Isocyanic ester is that this area is commonly used.As one or more the mixture in the modifier of aromatic diisocyanate, aromatic polyisocyanate or isocyanic ester.As tolylene diisocyanate (TDI), diphenylmethanediisocyanate (MDI) or polymethylene multi-phenenyl isocyanate (PAPI) etc.; The modifier of isocyanic ester can be liquefied mdi, as the liquefied mdi of carbodiimide modification.
Softening agent can be the ester that aromatic series or aliphatic dibasic alcohol and lipid acid generate, as dibutyl phthalate, dioctyl phthalate (DOP), dioctyl succinate, Octyl adipate or dioctyl sebacate (DOS) etc.
Organic amine curing agent is meant the aromatic diamine or derivatives thereof, comprise 3,5-diformazan sulfenyl tolylene diamine (DMTDA), 2,4-diamino-3,5-diformazan sulfenyl chlorobenzene (TX-2), 2,4-diamino-3-methylthio group-5-propyltoluene (TX-3), 3, the mixture of one or more in the 5-diethyl toluene diamine (DETDA) etc.
Photostabilizer can be benzophenone class or benzotriazole compound.As 2,4 dihydroxyl benzophenone, 2-hydroxyl-4-methoxy benzophenone, Octabenzone or 2-(2 '-hydroxyl-3 ', 5 '-two uncle's phenyl)-5-chlorination benzotriazole etc.
Flow agent can be acrylate or organo-siloxane base polymer, as BYK-S706, and preferred 0.1～0.5 part of add-on.
Defoamer can be the silicane defoamer, preferred 0.1～0.5 part of add-on.
The preparation method of polyurethane resin composition of the present invention comprises following steps:
(1) A component preparation: isocyanic ester, the softening agent of metering are added in the reactor, hydroxy-terminated polybutadienes or hydrogenation hydroxy-terminated polybutadienes that slow adding has been dewatered react 1.5～2h, sampling analysis isocyano (NCO) content down at 75～80 ℃, cooling discharge seals standby.The NCO massfraction is 2.8%～4.2%.
(2) B component preparation: amine curing agent, defoamer, photostabilizer, the flow agent of metering are mixed 1h down at 50 ± 3 ℃, and the discharging sealing is preserved.
With the mixed that polyurethane resin composition of the present invention is pressed A, B component mass ratio 100: 6～10, self-vulcanizing, mixed solution performance and gained mould material performance see Table 1 respectively, table 2.The performance index detection method is seen: the provisional technical qualification of Line for Passenger Transportation CRTS I template formula ballastless track convex retaining platform filled polyurethane resin (CPU) (No. (2008) 74, science and technology base), author: the Ministry of Railways, press: China Railway Press, the date of publication: 200806, book number 151132776.
Table 1 urethane resin mixed solution performance
Table 2 urethane resin mould material performance
Polyurethane resin composition of the present invention is mixed in proportion, and is cast between ballastless track of high-speed railway convex blocking platform and track plate half round cut, satisfies the service requirements of high-speed railway Line for Passenger Transportation non-fragment orbit after the self-vulcanizing.
Be main raw material with hydroxy-terminated polybutadienes or hydrogenation hydroxy-terminated polybutadienes in this polyurethane composition, and by in urethane resin, adding softening agent cheap and easy to get, make the gained polyurethane material have low shrinking percentage, have mechanical property and processing performance preferably simultaneously, reduced cost again.
Description of drawings
Fig. 1 is a boss resin dosing equipment state vertical view.
1-convex blocking platform 2-foamed polyethylene 3-boss potting resin
Fig. 2 is a boss resin dosing equipment state profile.
1-convex blocking platform 2-foamed polyethylene 3-boss potting resin
4-concrete foundation 5-cement asphalt mortar
Embodiment
The present invention will be further described below in conjunction with embodiment.
Embodiment is raw materials used as follows:
TDI-80/20:2,4-TDI and 2,6-TDI is with 80: 20 mixture of mass ratio;
GE-220: average functionality 2, number-average molecular weight are 2000 polyoxypropyleneglycol;
Flow agent BYK-S706: German Bi Ke chemical company product;
Defoamer BYK-A530: German Bi Ke chemical company product;
Hydroxy-terminated polybutadienes polyvalent alcohol P1: number-average molecular weight is 1500;
Hydroxy-terminated polybutadienes polyvalent alcohol P2: number-average molecular weight is 2700;
Hydrogenation hydroxy-terminated polybutadienes polyvalent alcohol: number-average molecular weight is 3100.
Material performance test method is by the regulation sample preparation and the test of [2008] No. 74 provisional technical qualification of Line for Passenger Transportation CRTS I template formula ballastless track convex retaining platform filled polyurethane resin (CPU) of science and technology base.
Comparative Examples 1:
In the there-necked flask that has agitator, thermometer, vacuum adapter, add polyoxypropyleneglycol GE-220100g (hydroxyl value is 56.1mgkOH/g), dibutyl phthalate (DBP) 23.7g, start agitator, vacuum pump, in about 100 ℃ the dehydration, be cooled to 50～60 ℃ standby.18.5g TDI is added in the reaction flask, slowly add the above-mentioned polyol component that has dewatered, at 75～80 ℃ of reaction 2h down, sampling analysis isocyano massfraction is 3.33%, be cooled to 50～60 ℃ of dischargings pack the A component.
In there-necked flask, add DMTDA 69g, BYK-S706 0.3g, BYK-A530 0.1g, Tinuvin B750.2g, mix 1h, be cooled to 40～50 ℃ of dischargings and get the B component at 40～50 ℃.
With A component 300g, B component 24.3g, stir 5min in mixed at room temperature, inject mould, ambient cure 28d tests every performance.
Embodiment 1-4:
Add the polyvalent alcohol of metering in having the there-necked flask that agitator, thermometer, vacuum take over, dioctyl sebacate (DOS) starts agitator, vacuum pump, dehydration in about 100 ℃, be cooled to 50～60 ℃ standby.The isocyanic ester of metering is added in the reaction flask, slowly adds the above-mentioned polyol component that has dewatered, at 75～80 ℃ of reaction 1.5-2h down, sampling analysis isocyano massfraction, be cooled to 50～60 ℃ of dischargings pack the A component.
Adding DMTDA 69g, BYK-S706 0.3g, BYK-A530 0.1g, Tinuvin B750.2g mix 1h at 40～50 ℃ in there-necked flask, are cooled to 40～50 ℃ of dischargings and get the B component.
With A, B component in proportion, stir 5min, inject mould in mixed at room temperature.Sample ambient cure 28d with the sulfuration back demoulding tests every performance.The proportioning raw materials of embodiment sees Table 3, and test-results sees Table 4.
Table 3 embodiment proportioning raw materials
| Comparative Examples 1 | |
|
|
|
|
| Hydroxy-terminated polybutadienes polyvalent alcohol P1 | / | 56.8 | / | 55.5 | / |
| Hydroxy-terminated polybutadienes polyvalent alcohol P2 | / | / | 59.3 | / | / |
| Hydrogenation hydroxy-terminated polybutadienes polyvalent alcohol | / | / | / | / | 59.2 |
| DBP | 23.7 | / | / | / | / |
| GE-220 | 100 | / | / | / | / |
| DOS | / | 31.0 | 31.0 | 27.8 | 29.4 |
| TDI-80/20 | 18.5 | 12.2 | 9.7 | / | 11.4 |
| MDI | / | / | / | 16.7 | / |
| NCO content/% | |||||
| DMTDA | 11.5 | 7.2 | 7.2 | 6.0 | 9.7 |
| A/B | 100/8.1 | 100/7.2 | 100/7.2 | 100/6 | 100/9.7 |
Table 4 embodiment result
| Test event | Comparative Examples 1 | |
|
|
|
| Hardness (shore A) | 81 | 82 | 81 | 83 | 78 |
| Coefficient of elasticity, kN/mm | 10.0 | 9.69 | 8.83 | 10.97 | 9.85 |
| Shrinking percentage (mm) | 15.0 | 4.08 | 2.76 | 3.79 | 3.23 |
Requirement by (2008) No. 74 literary compositions of science and technology base, through novel material inspection center of Nanche Zhuzhou Electric Locomotive Institute Co., Ltd embodiment 2 products are detected, the results are shown in Table 5, table 6, according to technical requirements in (2008) No. 74 literary compositions of science and technology base " the provisional technical qualification of passenger dedicated railway line CRTS I template formula ballastless track convex retaining platform filled polyurethane resin (CPU) " table 4.4 and the table 4.3, judge that this product is qualified.
The performance of table 5 mixed solution
| Sequence number | Interventions Requested | Technical | Unit | Assay | |
| 1 | Viscosity | ≤10 | Pa.s | 3.92 | |
| 2 | Operable time | ≥20 | | 35min37s | |
| 3 | Surface drying time | ≤24 | h | ＜3 | |
| 4 | The carrying time | ≤48 | h | ＜30 | |
| 5 | Cure shrinkage | ≤10 | mm | 2.76 |
The performance of table 6 pour mass
Claims (8)
1. polyurethane resin composition, thing comprises A, B two components, comprises following composition by mass parts:
(1) A component: 100 parts of hydroxy-terminated polybutadienes or hydrogenation hydroxy-terminated polybutadieness, 10～60 parts in softening agent, 15～30 parts of isocyanic ester;
(2) B component: 7～20 parts of organic amine curing agent, 0～5 part of photostabilizer, 0～2 part of flow agent, 0.1～0.5 part of defoamer;
The mass ratio of A, B component is 100: 6～10.
2. polyurethane resin composition according to claim 1, the molecular weight that it is characterized in that hydroxy-terminated polybutadienes or hydrogenation hydroxy-terminated polybutadienes is 1500～4000.
3. polyurethane resin composition according to claim 2 is characterized in that isocyanic ester is one or more the mixture in the liquefaction modifier of aromatic diisocyanate, aromatic polyisocyanate or isocyanic ester; Softening agent is the ester of aromatic series or aliphatic dibasic alcohol and lipid acid generation; Organic amine curing agent is meant the aromatic diamine or derivatives thereof; Photostabilizer is benzophenone class or benzotriazole compound; Flow agent is acrylate or organo-siloxane base polymer; Defoamer is the silicane defoamer.
4. polyurethane resin composition according to claim 3 is characterized in that nail phenylene diisocyanate, diphenylmethanediisocyanate or polymethylene multi-phenenyl isocyanate; The liquefaction modifier of isocyanic ester is a liquefied mdi; Softening agent is dibutyl phthalate, dioctyl phthalate (DOP), dioctyl succinate, Octyl adipate or dioctyl sebacate; Organic amine curing agent is 3,5-diformazan sulfenyl tolylene diamine, 2,4-diamino-3,5-diformazan sulfenyl chlorobenzene, 2,4-diamino-3-methylthio group-5-propyltoluene, 3, the mixture of one or more in the 5-diethyl toluene diamine; Photostabilizer is 2,4 dihydroxyl benzophenone, 2-hydroxyl-4-methoxy benzophenone, Octabenzone or 2-(2 '-hydroxyl-3 ', 5 '-two uncle's phenyl)-5-chlorination benzotriazole; The flow agent add-on is 0.1～0.5 part; The defoamer add-on is 0.1～0.5 part.
5. polyurethane resin composition according to claim 4 is characterized in that A, B component mixed solution have following performance: viscosity≤10Pa.s; Operable time 〉=20min; Surface drying time≤24h; Carrying time≤48h; Cure shrinkage≤10mm.
6. polyurethane resin composition according to claim 5 is characterized in that the gained mould material has following performance:
Outward appearance: surfacing, there are not obvious impurity, bubble, fold, crackle;
Apparent density: 〉=1.05 * 10
3Kg/cm
3
Hardness (Shao C): 〉=50 degree;
Coefficient of elasticity: 10 ± 2kN/mm;
Shearing resistance: 〉=2.0MPa;
Cohesive strength: 〉=0.50MPa;
Fatigue property: tension set≤1.2mm, the coefficient of elasticity velocity of variation is in ± 20%, and outward appearance is no abnormal;
Erosion resistance and heat-resistant aging: outward appearance is no abnormal, and the coefficient of elasticity velocity of variation is in ± 20%;
Temperature limit of brittleness :≤-50 ℃;
The cold-resistant coefficient of compression: 〉=0.50.
7. the preparation method of the described polyurethane resin composition of one of claim 1～6 comprises following steps:
(1) A component preparation: isocyanic ester, the softening agent of metering are added in the reactor, add the hydroxy-terminated polybutadienes or the hydrogenation hydroxy-terminated polybutadienes that have dewatered, react 1.5～2h down at 75～80 ℃, sampling analysis isocyano massfraction, cooling discharge, seal standbyly, NCO content is 2.8%～4.2%;
(2) B component preparation: amine curing agent, defoamer, photostabilizer, the flow agent of metering are mixed 1h down at 50 ± 3 ℃, and the discharging sealing is preserved.
8. the application of the described polyurethane resin composition of one of claim 1～6 on ballastless track of high-speed railway.
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| CN105273158A (en) * | 2015-11-16 | 2016-01-27 | 烟台德邦科技有限公司 | Synthetic method for low-shrinkage rate butyl hydroxy type polyurethane |
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| CN105273158A (en) * | 2015-11-16 | 2016-01-27 | 烟台德邦科技有限公司 | Synthetic method for low-shrinkage rate butyl hydroxy type polyurethane |
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