CN103923457B - A kind of High-abrasion-resistpolyurethane polyurethane elastomer and preparation method thereof - Google Patents
A kind of High-abrasion-resistpolyurethane polyurethane elastomer and preparation method thereof Download PDFInfo
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- CN103923457B CN103923457B CN201410124324.6A CN201410124324A CN103923457B CN 103923457 B CN103923457 B CN 103923457B CN 201410124324 A CN201410124324 A CN 201410124324A CN 103923457 B CN103923457 B CN 103923457B
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Abstract
The invention discloses a kind of High-abrasion-resistpolyurethane polyurethane elastomer and preparation method thereof, be made up of performed polymer component (component A) and chain extender component (B component) two parts, component A in parts by weight by 100 parts of polyester or polyether polyol, 15～30 parts of TDI, 0～20 part of softening agent, 0.5～2 Organic Friction-Reducing agent, 2～10 gas-phase silica form；B component is hybrid diamine class chain extender, by methyl double (3 chlorine 2,6 diethylaniline) (MCDEA) and other Diamines mixture of chain extenders composition.Material of the present invention has anti-wear performance and the mechanical property of excellence, can be used for preparing the product in the preparation equipment fields such as polyurethane sieve plate, screen cloth, conveyer belt.
Description
Technical field
The present invention relates to polyurethane elastomer and preparation method thereof, particularly to anti-wear performance and the mechanical property with excellence
The polyurethane products of energy.
Background technology
Polyurethane sieve plate and screen cloth are the work surfaces of ore sizing, and in running, sieve plate and screen cloth are produced by material
Sliding friction, rolling friction, impacting, wear and tear and the effect such as corrosion, work under bad environment, the anti-wear performance of sieve plate and screen cloth is shadow
Ringing the key factor in its service life, the material for polyurethane sieve plate and screen cloth is usually polyester/toluene two in the market
Isocyanates (TDI)/4,4 '-diaminourea-3,3 '-two dichloro diphenyl methanes (MOCA) system, its abrasion (DIN53516) are general
More than 50mm3, it is usually three to six months service life.
Polyurethane material is in actual use typically by changing raw material or to add wear-resistant auxiliary agent or filler resistance to improve
Mill performance.Hu Fengwei, the Ge Tiejun .MCDEA impact [J] on polyurethane elastomer wearability. innovation Shenyang collected works, 262-266,
Use PTMG and TDI-80 to synthesize performed polymer, respectively with MOCA and MCDEA chain extension, investigate two kinds of chain extenders to elastomer wearable
The impact of performance, under the same terms, MCDEA is better than MOCA wearability.Tao Haitao. the preparation of modified HTBN type polyurethane elastomer
And performance study [D]. Qiqihar University 2011, resistance to elastomer to graphite in EU and molybdenum bisuphide addition
The impact of mill performance is studied, and the anti-wear performance of material improves little.Liu Fang, Wu little Hua, Liu Anshi, etc. anti-attrition is wear-resisting poly-
The research [J] of urethane composite frictional behaviour. plastics industry, 1997 (4): 76-78 by adding in polyethers/TDI performed polymer
The additive entering to have anti-attrition function carries out physical blending, uses MOCA chain extension, investigates wear reducing additive to material wear-resistant performance
Impact, result shows: organosilicon and organic wax class additive are preferable with the sizing material compatibility, can be obviously improved material wear-resistant performance,
And wearability is improved inconspicuous and poor with the compatibility of sizing material by fluorine material and inorganic filler, system occurs significantly
It is separated.
Patent documentation CN102264786A discloses a kind of shoe press belt, and it includes by the prepolymer containing isocyanate groups
The polyether polyols with reduced unsaturation prepared with chain extender blend, this prepolymer is to prepare with PPDI (PPDI), and this expansion
Chain agent blend includes methyl-bis-(3-chloro-2,6-diethyl-aniline) (MCDEA), and its raw material PPDI used is expensive.
Patent documentation CN103254387A discloses a kind of High-abrasion-resistpolyurethane polyurethane elastomer and preparation method thereof, and this invention is led to
Crossing the ethylene powder adding super high molecular weight, improve wearability and the hot strength maximum 27.9 of elastomer, abrasion are more than
100mm3/1000m。
Summary of the invention
First technical problem that the invention solves the problems that is to provide a kind of High-abrasion-resistpolyurethane polyurethane elastomer, and this elastomer has
Excellent anti-wear performance and mechanical property.
Second technical problem that the invention solves the problems that is to provide the preparation side of a kind of High-abrasion-resistpolyurethane polyurethane elastomer material
Method.
The High-abrasion-resistpolyurethane polyurethane elastomer material of the present invention is by performed polymer component (component A) and chain extender component (B component)
Two parts form:
(1) component A, in parts by weight:
Organic Friction-Reducing agent is organosilicon, Organic fluoride or one or more mixture of organic wax class, such as have methyl-silicone oil,
Fluorine carbon emulsion or liquid paraffin etc..Gas-phase silica specific surface area is 150～380m2/ g is preferable, the A200 of such as EVONIK,
A380 etc..
Wherein polyester or the preferred polyester diol of polyether polyol, PolyTHF dihydroxylic alcohols (PTMG), Merlon two
Unit's alcohol (PCD) or a combination thereof.Polyester diol preferred number average molecular weight be 1000-3000 polyadipate system polyester diol,
Polycaprolactone diols (PCL).PolyTHF dihydroxylic alcohols (PTMG) preferred number average molecular weight 1000-3000.
Softening agent is diethyl phthalate (DEP), dibutyl phthalate (DBP), dioctyl phthalate
(DOP), DMEP (DMEP), BBP(Butyl Benzyl Phthalate (BBP), diethylene glycol dibenzoate
(DEG), one or more in dipropylene glycol dibenzoate (DPG) etc. blend.
(2) B component is hybrid diamine class chain extender, by methyl-bis-(3-chloro-2,6-diethyl-aniline) (MCDEA) and its
He forms by Diamines mixture of chain extenders, and wherein MCDEA is preferably 0.5～1.5: 1 with the mol ratio of other diamine chain stretching agents, its
His diamine chain stretching agent can be selected for 4,4 '-diaminourea-3,3 '-dichloro diphenyl methane (MOCA), 3,5-dimethythiotoluene diamine
Or one or more the mixture such as diethyl toluene diamine (DETDA) (DMTDA).
The preparation method of the High-abrasion-resistpolyurethane polyurethane elastomer material of the present invention, comprises the following steps:
(1) preparation of component A: by polyester or polyether polyol, softening agent, Organic Friction-Reducing agent and gas-phase silica, by based on
Amount adds reactor stirring, mixes 0.5～1h, after carrying out secondary mixing dispersion by ball mill, adds reactor, and material temperature rises to
120～130 DEG C, vacuum dehydration 2～3h, after cooling add TDI, reaction temperature controls at 75～95 DEG C, the response time be 1.5～
2h, vacuum defoamation, cooling discharge, seal and preserve；
(2) preparation of B component: respectively by after different amine chain extender heating and melting, according to corresponding mixed in molar ratio
Rear standby；
(3) preparation of elastomer: material cast can use hand dropping or machine cast, and chain extension coefficient is 0.9～0.95,
Component A temperature 70～90 DEG C, B component temperature 100～130 DEG C, mold temperature 100～120 DEG C, gel time 4～8min, the demoulding
Time 20～40min, after cure temperature is 100～120 DEG C, cure time 12～16h.
The inventive method gained elastomer performance is shown in Table 1.
Table 1 elastomer performance
| Hardness/Shao A | 92～97 |
| Gel time/min | 4～7 |
| Demoulding time/min | 20～40 |
| Hot strength/MPa | 45～60 |
| Tearing strength/N/mm | 100～120 |
| Percentage elongation/% | 400～550 |
| Abrasion/mm3 | <30 |
The present invention uses being used in conjunction with of gas-phase silica and Organic Friction-Reducing agent, improves organic auxiliary agent in material
Dispersing uniformity, is integrally improved the anti-wear performance of material.The material invented has anti-wear performance and the mechanical property of excellence,
Can be used for preparing the product in the preparation equipment fields such as polyurethane sieve plate, screen cloth, conveyer belt.
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further described, is not limited to the present invention.
PEPA LM2456 is the adipate glycol butanediol ester PEPA that Liming chemical Inst produces,
Molecular weight 2000；PEPA LM2856 is the adipate glycol propylene glycol ester polyester polyols that Liming chemical Inst produces
Alcohol, molecular weight 2000；PTMG-1000 is PolyTHF, and molecular weight is 1000.
Embodiment 1
The synthesis of component A: first by 1000g PEPA LM2456,100gDEP, 10g methyl-silicone oil and 30g white carbon
After mixing, add ball mill and carry out secondary mixing dispersion, then take 585g and add reactor, be heated to 125 DEG C, dehydrated under vacuum
After 2h, material temperature is down to 70 DEG C, add 220gTDI, 75 DEG C, nitrogen protection under react 2h.
The preparation of B component: be to mix homogeneously at 1: 0.5 in molar ratio after MOCA with MCDEA is melted respectively.
The preparation of elastomer: by A, B component according to the chain extension coefficient mixing deaeration of 0.93 after, pour into 100 DEG C of 2mm moulds,
The 40min demoulding, 125 DEG C of after cure 12h, room temperature surveys performance after placing 7 days.Resulting materials performance is shown in Table 2.
Embodiment 2
The synthesis of component A: after first 1000gPTMG-1000,20g fluorine carbon emulsion and 60g white carbon being mixed, add ball milling
Machine carries out secondary mixing dispersion, then takes 510g and adds reactor, is heated to 120 DEG C, after dehydrated under vacuum 2h, material temperature is down to
70 DEG C, add 242gTDI, 95 DEG C, nitrogen protection under react 1.5h.
The synthesis of B component: be to mix homogeneously at 1: 1.5 in molar ratio after MOCA with MCDEA is melted respectively.
The preparation of elastomer: by A, B component according to the chain extension coefficient mixing deaeration of 0.9 after, pour into 120 DEG C of 2mm moulds,
The 20min demoulding, 100 DEG C of after cure 16h, room temperature surveys performance after placing 7 days.Resulting materials performance is shown in Table 2.
Comparative example 1
The synthesis of component A: add 500g PEPA LM2856 in the reactor and be heated to 100-110 DEG C, under vacuum
Dehydration 3h after, material temperature is down to 70 DEG C, add 100gTDI, 80 DEG C, nitrogen protection under react 3h make reaction complete.
The preparation of B component: be to mix homogeneously at 1: 0.5 in molar ratio after MOCA with MCDEA is melted respectively.
The preparation of elastomer: by A, B component according to the chain extension coefficient mixing deaeration of 0.93 after, pour into 100 DEG C of 2mm moulds,
The 40min demoulding, 100 DEG C of after cure 16h, room temperature surveys performance after placing 7 days.Resulting materials performance is shown in Table 2.
Table 2 embodiment material property
| Test event | Embodiment 1 | Embodiment 2 | Comparative example 1 |
| Hardness/Shao A | 91 | 95 | 91 |
| Gel time/min | 7 | 4 | 6.5 |
| Demoulding time/h | 40 | 20 | 35 |
| Hot strength/MPa | 46 | 52 | 45 |
| Tearing strength/N/mm | 103 | 110 | 105 |
| Percentage elongation/% | 460 | 520 | 480 |
| Abrasion/mm3 | 28 | 24 | 43 |
Claims (10)
1. a High-abrasion-resistpolyurethane polyurethane elastomer, by performed polymer component (component A) and chain extender component (B component) two parts group
Become:
(1) component A, in parts by weight:
(2) B component is hybrid diamine class chain extender, by methyl-bis-(3-chloro-2,6-diethyl-aniline) (MCDEA) and other two
Amine chain extender mixture forms.
High-abrasion-resistpolyurethane polyurethane elastomer the most according to claim 1, is characterized in that Organic Friction-Reducing agent refers to organosilicon, organic
Fluorine or one or more mixture of organic wax class.
High-abrasion-resistpolyurethane polyurethane elastomer the most according to claim 2, it is characterized in that Organic Friction-Reducing agent referred to methyl-silicone oil,
Fluorine carbon emulsion or liquid paraffin, gas-phase silica specific surface area is 150～380m2/g。
High-abrasion-resistpolyurethane polyurethane elastomer the most according to claim 1, is characterized in that polyester or polyether polyol refer to polyester
Dihydroxylic alcohols, PolyTHF dihydroxylic alcohols (PTMG), PCDL (PCD) or a combination thereof.
High-abrasion-resistpolyurethane polyurethane elastomer the most according to claim 4, is characterized in that polyester diol is number average molecular
Polyadipate system polyester diol, polycaprolactone diols (PCL) for 1000-3000；PolyTHF dihydroxylic alcohols (PTMG)
Number-average molecular weight is 1000-3000.
High-abrasion-resistpolyurethane polyurethane elastomer the most according to claim 1, is characterized in that softening agent is diethyl phthalate
(DEP), dibutyl phthalate (DBP), dioctyl phthalate (DOP), DMEP
(DMEP), BBP(Butyl Benzyl Phthalate (BBP), diethylene glycol dibenzoate (DEG), dipropylene glycol dibenzoate (DPG)
In one or more blend.
High-abrasion-resistpolyurethane polyurethane elastomer the most according to claim 1, is characterized in that rubbing of MCDEA and other diamine chain stretching agents
Your ratio preferably 0.5～1.5: 1, other diamine chain stretching agents are 4,4 '-diaminourea-3,3 '-dichloro diphenyl methane (MOCA), 3,5-
One or more mixture of dimethythiotoluene diamine (DMTDA) or diethyl toluene diamine (DETDA).
8. the method preparing the described High-abrasion-resistpolyurethane polyurethane elastomer of one of claim 1～7, comprises the following steps:
(1) preparation of component A: by polyester or polyether polyol, softening agent, Organic Friction-Reducing agent and gas-phase silica, add by metering
Entering reactor stirring, mix 0.5～1h, after carrying out secondary mixing dispersion by ball mill, add reactor, material temperature rises to 120
～130 DEG C, vacuum dehydration 2～3h, add TDI after cooling, reaction temperature controls at 75～95 DEG C, and the response time is 1.5～2h,
Vacuum defoamation, cooling discharge, seal and preserve；
(2) preparation of B component: respectively by after different amine chain extender heating and melting, uniform according to corresponding mixed in molar ratio
The most standby；
(3) preparation of elastomer: material cast can use hand dropping or machine cast, and chain extension coefficient is 0.9～0.95, A group
Point temperature 70～90 DEG C, B component temperature 100～130 DEG C, mold temperature 100～120 DEG C, gel time 4～8min, during the demoulding
Between 20～40min, after cure temperature is 100～120 DEG C, cure time 12～16h.
The method of preparation High-abrasion-resistpolyurethane polyurethane elastomer the most according to claim 8, is characterized in that gained elastomer has
Following performance:
The method of preparation High-abrasion-resistpolyurethane polyurethane elastomer the most according to claim 8 or claim 9, is characterized in that gained elastomer
Can be used for preparing polyurethane sieve plate, screen cloth or conveyer belt.
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| CN104231222B (en) * | 2014-09-19 | 2017-07-07 | 黎明化工研究设计院有限责任公司 | A kind of High-abrasion-resistpolyurethane polyurethane elastomer and preparation method thereof |
| CN104530381A (en) * | 2014-12-29 | 2015-04-22 | 成都瑞吉龙科技有限责任公司 | Coated insulating material for overall insulation of railway switch installation device |
| CN104830051A (en) * | 2015-05-18 | 2015-08-12 | 吴江市宏宇机械有限公司 | Novel polyurethane elastomer for mold resins and preparation method thereof |
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Effective date of registration: 20170523 Address after: 519000, B14-2 building, 5 floor, No. 333 Bauhinia Road (Shishan building), Zhuhai, Guangdong, Xiangzhou Patentee after: Zhuhai MEIKO Technology Co., Ltd. Address before: 471000 Wangcheng Avenue, Henan, Luoyang, No. 69 Patentee before: Liming Research Institute of Chemical Industry Co.,Ltd. |