CN106397706A - High-hardness epoxy modified polyurethane composite material and preparation method thereof - Google Patents
High-hardness epoxy modified polyurethane composite material and preparation method thereof 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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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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
- C08G18/08—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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- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
- C08G18/6677—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
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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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Abstract
The invention relates to a high-hardness epoxy modified polyurethane composite material, which is prepared by adding a component A and a component B into a vacuumable sealed container and carrying out a mixed reaction by using a prepolymer method, wherein the component A is a mixture of a terminal isocyanate prepolymer and an epoxy resin, and the component B is a mixture of a chain extender and a catalyst. The preparation method comprises: weighing 130-140 parts of the component A and 2.4-15.2 parts of the component B, respectively pre-heating, adding the pre-heated components A and B to a vacuumable sealed container, mixing, carrying out vacuum deaeration while stirring, taking out after the gas bubbles are completely removed, pouring into a corresponding mold, carrying out low temperature curing, demolding, and carrying out heating vulcanization to prepare the high-hardness epoxy modified polyurethane composite material. According to the present invention, the product has advantages of high toughness, prolonged service life in the kettle, controllable reaction speed, low cost, and the like.
Description
Technical field
The invention belongs to organic elastomeric polymer material and its preparing technical field, more particularly, to a kind of modified polyurethane composite
And preparation method thereof.
Background technology
High rigidity (ShoreD hardness >=70) polyurethane elastomer is widely used in pressure roll, bearing, gear, stamping die, guarantor
Age ball etc., but because polyurethane elastomer material hardness number is high, hard segment content is high, all there is skill in terms of technique and material property
An art difficult problem.In the preparation of polyurethane elastomer material, mainly elastomer is improved by the method for raising hard segment content at present hard
Degree.For prepolymer method, improving hard segment content must increase isocyanates and chain extender consumption, generally as different
Cyanate and the increase of chain extender consumption, polyurethane material hardness has certain rising, but its chain extending reaction speed can be greatly improved,
Reaction speed is fast, and the lost of life in kettle is not easy to operate；Simultaneously in the aspect of performance of product, material fragility increases, and toughness declines,
Seriously limit it to use and promote.Test shows, will prepare the polyurethane elastomer that Shao's D hardness is more than 75D, NCO matter
Amount fraction should be higher than that 10%, and the gel time of this high NCO content system is less than 1min, seriously limits it and uses and push away
Extensively.A kind of hardness height, good toughness how are obtained, there is the polyurethane elastomer material in life-span in longer kettle are simultaneously always ability
The technological difficulties that field technique personnel needs are captured.
Pan Guangjun etc. (Qingdao University of Science and Technology's journal, 2008,29 (4):334-336) utilize epoxy resin (E-51) and poly- ammonia
Ester prepolymer reaction, is prepared for epoxy resin modification polyurethane elastomer material.This technical scheme is first by PPG PTMG
Mix latter 100 DEG C～110 DEG C with epoxy resin E-51 and vacuumize dehydration, be then cooled to 50 DEG C～60 DEG C, add toluene two
React 2.5h, prepared base polyurethane prepolymer for use as component under the conditions of 90 DEG C～95 DEG C after isocyanates (TDI-100), be subsequently adding
A certain amount of 3,3 '-two chloro- 4,4- diaminodiphenyl-methanes, several catalyst of triethylamine, the rear mold that stirs suppresses to obtain ring
Oxygen tree fat modified polyurethane elastomer material.The epoxy resin modification polyurethane elastomer material hardness range of this technical scheme preparation
Between Shao A92～98, hardness number is low.On synthesis technique, epoxy resin E-51 and PPG simultaneously participate in and
The polymerisation of toluene di-isocyanate(TDI) (TDI-100), exist reaction acutely, the performed polymer material viscosity of synthesis big the shortcomings of, should
Technical scheme is not suitable for carrying out the preparation of High Hardness Polyurethane Elastomer.
CN 101550327A Chinese patent literature discloses a kind of high hardness high-toughness polyurethane casting compound and its application, and it is by A
Component and B component mix acquisition by a certain percentage, and component A is by the end isocyanide of isocyanates and polyethers or PEPA synthesis
Acid esters performed polymer, B component is less than 400 two degrees of functionality or the polyalcohol of three-functionality-degree for molecular weight, or is less than by molecular weight
400 small molecule polyol is mixed to prepare in 1000～2000 macromolecular PPG or PEPA with molecular weight.To the greatest extent
Manage the prepared material product of this technical scheme and there is the characteristics such as hardness height, good toughness, but be not directed to use in this technical scheme
The technique thinking of epoxy resin modification polyurethane material, it is compared to high hard using epoxy resin modification polyurethane elastomer gained
For degree material, its high expensive.
CN 103524703A Chinese patent literature discloses a kind of preparation method of polyurethane/epoxy resin composites, its master
To be obtained by component A and B component mixing, component A is base polyurethane prepolymer for use as, by PPG N210 and diphenyl methane
Diisocyanate MDI-50 synthesizes prepared under certain condition, and the epoxy resin that B component blocks for binary arylamine, by disulfide group
Toluenediamine or 2,4- diaminourea -3, reaction under 5- dimethyl sulphur-based chlorobenzene and epoxy resin E-44 certain condition is obtained, component A and B
Component reacts curing molding after mixing according to a certain percentage under normal temperature condition, has prepared and has had performance preferably gluing agent material.
However, the purpose of this technical scheme is mainly for the preparation of adhesive for polyurethane material, hardness is low, and molding mode is normal temperature cure,
The cured later time is long, and efficiency is low.
Additionally, CN 104119499A Chinese patent literature discloses a kind of preparation method of epoxide modified aromatic series polythiourethane,
CN 104119497A Chinese patent literature discloses a kind of preparation method of epoxide modified aliphatic poly thiourethane, CN
102010498A Chinese patent literature discloses a kind of elastic polyurethane preparation meeting water rapid expanding.
From the point of view of prior art disclosed above, all there is following major defect：1) existing modified polyurethane material hardness number is all little
Shao Yu 50D is it is impossible to meet the use requirement of certain applications；2) in the formula of existing employing or technique, adding epoxy
After resin modified, polyurethane material hardness number improves and inconspicuous；3) in prior art, most epoxy resin ring-opening reaction is solid
Agent and the selection of catalyst, are all inclined to use amine curing agent and participate in epoxy ring opening reaction, during curing reaction there be the overwhelming majority
There is ring-opening reaction using diamine (MOCA) chain extender and epoxy resin, after forming amido end-blocking epoxy resin, then with poly-
Urethane performed polymer participates in reaction, using this technical scheme when preparing high hardness material, due to the high reaction activity of amido, can produce
Raw reaction speed is fast, the problem of manufacturability difference, is also not suitable for carrying out the cast of larger product；4) portion of techniques scheme does not then add
Enter corresponding chain extender component, so can lead to toughness of material wretched insufficiency.
Therefore, not only product hardness is low for the epoxy modified polyurethane elastomeric material of existing preparation, and process efficiency low,
High cost, operation are difficult to control to, and there is no high rigidity (ShoreD hardness >=70) epoxy modified polyurethane composite to prepare at present
Relevant report,
Content of the invention
The technical problem to be solved is to overcome the shortcomings of to mention and defect in background above technology, provide one kind to have
The high rigidity epoxy modified polyurethane composite of life in high tenacity, kettle, correspondingly provide a kind of reaction speed controlled,
Cost reduces, the preparation method of the high rigidity epoxy modified polyurethane composite of step more simplification.
For solving above-mentioned technical problem, technical scheme proposed by the present invention is a kind of high rigidity epoxy modified polyurethane composite,
Described epoxy modified polyurethane composite is by component A and B component being added to the airtight of vacuum-pumping using prepolymer method
Prepare after carrying out hybrid reaction in container；Described component A is the mixture of isocyanate terminated performed polymer and epoxy resin；Institute
With B component for the mixture of chain extender and catalyst.
Above-mentioned high rigidity epoxy modified polyurethane composite is it is preferred that the Shore of described epoxy modified polyurethane composite
D hardness >=70.
Above-mentioned high rigidity epoxy modified polyurethane composite is it is preferred that the stretching of described epoxy modified polyurethane composite
Intensity >=35MPa, elongation at break >=12%, bending strength >=40MPa, impact strength >=100KJ/m2.
As a total technology design, the present invention also provides a kind of system of above-mentioned high rigidity epoxy modified polyurethane composite
Preparation Method, comprises the following steps：
Weigh 130～140 parts of component A, 2.4～15.2 parts of B component, preheat respectively；Then by the component A after preheating and B
Component is added to mixing in the closed container of vacuum-pumping, carries out vacuum defoamation while stirring, takes out after bubble purifies, cast
To in corresponding mould, then carry out low-temperature setting, the demoulding, then heat sulfuration, prepared high rigidity epoxy modified polyurethane composite wood
Material (this step uses prepolymer method)；
Described component A is the mixture of isocyanate terminated performed polymer and epoxy resin；Described B component is chain extender and catalyst
Mixture.It should be strongly noted that the epoxy resin used by the present invention is the epoxy resin not carrying out holding amido end-blocking, because
Such epoxy resin can lead to that the reaction speed when preparing high hardness polyurethane material is fast, manufacturability is poor, and then does not enable this
The purpose of invention.
It is preferred that the preparation of described component A includes in above-mentioned preparation method：Under the conditions of 50 DEG C～80 DEG C, to 100 matter
In the amount isocyanate terminated performed polymer of part, (addition can be between 30～40 mass parts for the epoxy resin of interpolation 30～40 mass parts
Any number, such as 31 parts, 35 parts etc.), component A is obtained after fully mixing.The molal quantity of epoxy resin epoxide epoxy group group is pressed
Following computational methods：Epoxide group molal quantity=epoxy resin adds quality × epoxide number.
It is preferred that described isocyanate terminated performed polymer is nco value (NCO between 13%～16% in above-mentioned preparation method
Any number between value desirable 13%～16%, such as 13%, 14.6%, 16% etc.) isocyanate terminated performed polymer, described end
Isocyanate prepolymers body is prepared by after PPG and/or PEPA and polyisocyanates polymerisation；Described epoxy
Resin includes the mixture of one or more of E-54, E-51, E-44, E-42, E-35, E-31.It is furthermore preferred that it is described
PPG be PTMG, polypropylene oxide glycol, described PEPA includes polybutyleneadipate
Esterdiol, polycaprolactone glycol, polyethylene glycol adipate glycol, polyadipate ethylene glycol and 1,2-propylene glycol esterdiol, polyadipate
Diglycol esterdiol, polyadipate -1,4- butyl glycol ester diol, polyadipate neopentyl glycol -1,6-HD esterdiol,
The mixture of one or more of PCDL.It is furthermore preferred that described polyisocyanates includes diphenyl methane -4,4 '
- diisocyanate (pure MDI), Carbodiimide-Modified MDI (liquefied mdi), MDI-50, toluene di-isocyanate(TDI) (TDI),
3,3 '-dimethyl diphenyl diisocyanate (TODI), PPDI (PPDI) or hydrogenated diphenyl methane two isocyanic acid
Ester (hydrogenation MDI).
Above-mentioned preparation method is it is preferred that the preparation of described isocyanate terminated performed polymer includes：Will be many for the polyethers of 100 mass parts
First alcohol and/or PEPA add reactor, keep vacuum in 0.09～0.1MPa, be dehydrated (one at 100 DEG C～130 DEG C
As 2～3h)；Then cool to 40 DEG C～60 DEG C, add the polyisocyanates of 48～188 mass parts, 80 DEG C of ± 5 DEG C of bars
Isothermal reaction 2～3h under part, cooling discharging, isocyanate terminated performed polymer is obtained.
Above-mentioned preparation method is it is preferred that the preparation of described B component includes：Under the conditions of 50 DEG C～80 DEG C, by measure
The catalyst of 2.4～15.2 parts of chain extender and 0.01～0.1 part is sufficiently mixed rear discharging.
Described chain extender is mixed to prepare with three-functionality-degree chain extender using two degrees of functionality of water content≤0.05%：
The molar fraction that described two degree of functionality chain extender consumptions account for chain extender total amount is 50%～80%；Described three-functionality-degree chain extender
The molar fraction that consumption accounts for chain extender total amount is 20%～50%；
Described two degree of functionality chain extenders include ethylene glycol, propane diols, butanediol, hexylene glycol, diglycol, methyl-prop two
At least one in alcohol, Isosorbide-5-Nitrae-cyclohexandiol, neopentyl glycol；Described three-functionality-degree chain extender includes glycerine, trihydroxy methyl third
At least one in alkane.Currently preferred chain extender selects two degree of functionality alcohols and three-functionality-degree alcohols chain extender, both can drop
Low material reaction speed, extends the operating time, can improve toughness of material again.
The consumption of above-mentioned preferred chain extender determines in the following manner：
Two degree of functionality chain extender consumptions=[(M/42) × 0.95- epoxide group molal quantity] × two degree of functionality chain extender molar fraction ×
Chain extender equivalent used；
Three-functionality-degree chain extender consumption=[(M/42) × 0.95- epoxide group molal quantity] × three-functionality-degree chain extender molar fraction ×
Chain extender equivalent used；
Wherein, M represents isocyano quality in isocyanate terminated performed polymer, the isocyanate terminated performed polymer quality × nco value of M=.
It is preferable that imidazoles catalyst selected by described catalyst in above-mentioned preparation method, more preferably use 2-methylimidazole, 2-
One of ethyl -4-methylimidazole, 2- phenylimidazole, 1- benzyl -2-methylimidazole, 1- 1-cyanoethyl-2-methylimidazole.This
The imidazoles catalyst of bright special selection, not only high catalytic efficiency, and the solidfied material of function admirable can be obtained at a lower temperature,
It is suitable to make large complicated product, be more beneficial for expanding the range of application of material.
Above-mentioned preparation method is it is preferred that described component A is controlled at 50 DEG C～80 DEG C with the preheating temperature of B component；Described true
The time control of empty deaeration is in 1～3min；The temperature of described low-temperature setting is 80 DEG C～100 DEG C, and hardening time is 1～2h；
Described plus heat-vulcanized temperature is 100 DEG C～120 DEG C, and cure time is 10～16h.
The technical scheme of the invention described above is based primarily upon following mechanism：Epoxy resin has excellent physical and mechanical properties, price phase
To cheap, it is widely used, due to containing epoxide group and oh group in its strand, these groups can enter with isocyanates
Row reaction, thus epoxy molecule chain can be incorporated in polyurethane segment, improves some performances of polyurethane material, significantly
Improve its hardness number.The present invention is directed to the defects such as short life, fragility in the kettle that existing high hardness polyurethane material exists is big, design
Epoxy resin is incorporated in polyurethane elastomer system as hard section, to obtain a kind of high rigidity, high tenacity and there is longer kettle
The modified polyurethane material in middle life-span.
Compared with prior art, it is an advantage of the current invention that：
1. the present invention passes through the hybrid reaction pattern using component A and B component, and component A is isocyanate terminated performed polymer and epoxy
The mixture of resin, B component is the mixture of chain extender and catalyst；And epoxy resin is to block at addition without end amido
Reason, the epoxy modified polyurethane composite tensile strength >=35MPa of final preparation, elongation at break >=12%, bending strength
>=40MPa, impact strength >=100KJ/m2, material hardness is high, good toughness, and combination property is superior.
2. the existing general epoxide group open loop participation reaction to be caused using amine curing agent or other catalyst in epoxy resin,
Do curing agent or catalyst using amine substance, have the shortcomings that during curing reaction, heat release is big, be not suitable for preparing the high hard of the present invention
Degree material；And the present invention selects imidazoles catalyst, such catalyst can realize catalytic action at a lower temperature, and is catalyzed
Excellent effect.
The present invention by specific process, epoxy resin is added in polyurethane system, solves existing high hardness polyurethane
Material improves with hardness, and then produces the lost of life in kettle, fragility increase, the technical problem of toughness decline；The present invention is obtained
Composite while there is high rigidity, high tenacity, reaction speed is adjustable, life in kettle, has expanded the poly- ammonia of high rigidity
The range of application of ester material.
Additionally, the preparation method of the present invention not only reaction speed is controlled, and cost reduces further, and step more simplifies, and produces
The scope of application of product further expands, and has preferable industrial prospect.
Specific embodiment
For the ease of understanding the present invention, below in conjunction with preferred embodiment, the present invention is made more comprehensively, meticulously to describe, but this
The protection domain of invention is not limited to embodiment in detail below.
Unless otherwise defined, all technical terms used hereinafter are identical with the implication that those skilled in the art are generally understood that.
Technical term used herein is intended merely to describe the purpose of specific embodiment, is not intended to limit the protection model of the present invention
Enclose.
Unless otherwise specified, the various raw material used in the present invention, reagent, instrument and equipment etc. all can be purchased by market
Can buy or can be prepared by existing method.
Embodiment 1：
A kind of high rigidity epoxy modified polyurethane composite of the present invention, Shore D hardness >=70 of this composite, this ring
Oxygen modified polyurethane composite is by component A and B component being added in the closed container of vacuum-pumping using prepolymer method
Prepare after carrying out hybrid reaction；Component A is the mixture of isocyanate terminated performed polymer and epoxy resin；B component is chain extension
Agent and the mixture of catalyst.
The preparation method of the above-mentioned high rigidity epoxy modified polyurethane composite of the present embodiment, specifically includes following steps：
1. prepare isocyanate terminated performed polymer
Isocyanate terminated performed polymer is prepared with polyisocyanates polymerisation using PPG and PEPA, specifically includes
Following steps：In terms of mass fraction, by the PTMG (PTMG, equivalent 1000, degree of functionality 2) of 24.1g and
The polycaprolactone glycol (PCL, equivalent 1000, degree of functionality 2) of 24.1g adds reactor, keeps vacuum to exist at 110 DEG C
Under the conditions of 0.09～0.1MPa, it is dehydrated 2h；Then cool to 60 DEG C, add the polyisocyanates of 51.8g, polyisocyanic acid
Ester selects Carbodiimide-Modified MDI (NCO content 29.0%), isothermal reaction 2h under the conditions of 80 DEG C, cooling discharging, is obtained
Nco value is 13% isocyanate terminated performed polymer.The reaction principle of this step is schematically as follows：
Because isocyanates is excessive, in the isocyanate terminated performed polymer therefore prepared, existing isocyanate-terminated macromolecular polyol
Also there is the methyl diphenylene diisocyanate having neither part nor lot in reaction.For ease of description, by two kinds of isocyanate terminated material molecule formula unifications
It is abbreviated as：OCN-RN-NCO.
2. prepare component A
Component A mixes acquisition by above-mentioned prepared isocyanate terminated performed polymer with epoxy resin, and the molecular formula of epoxy resin is as follows：
Specifically under the conditions of 70 DEG C, the isocyanate terminated performed polymer of above-mentioned prepared 100g adds 30g epoxy resin (ring
Oxygen tree fat selects E-51, epoxide number 0.51mol/100g) mixing acquisition afterwards, according to epoxy addition and epoxide number, calculate
Epoxy radicals molal quantity is 0.153mol.
3. prepare B component
The preparation of B component is under the conditions of 60 DEG C, and by 5.08g BDO, (degree of functionality 2, equivalent 45, molar fraction take
80%), 1.27g trimethylolpropane (TMP, degree of functionality 3, equivalent 45, molar fraction take 20%) and 0.03g catalyst
(selecting 2-methylimidazole) is sufficiently mixed rear discharging, altogether 6.38g.Two degrees of functionality and three-functionality-degree chain extender molecular formula are such as
Under：
The quality of required chain extender calculates in such a way：
1,4- butanediol quality=[(13/42) × 0.95-0.153] × 0.8 × 45=5.08g
TMP mass=[(13/42) × 0.95-0.153] × 0.2 × 45=1.27g.
4.A component is mixed with B component
It is separately heated to 60 DEG C by weighing good above-mentioned 130g component A with 6.38g B component raw material, be added to the close of vacuum-pumping
Close mixing in container, vacuumize 1～3min while stirring, take out after bubble purifies, be poured in mould, under the conditions of 80 DEG C
The demoulding after solidification 1h, then under the conditions of 100 DEG C, after cure 16h, prepared high rigidity, high-toughness polyurethane epoxy composite material
Material.The molecular formula of this epoxy modified polyurethane composite is typically shown below.
Gel time according to the high rigidity of above-described embodiment preparation, high tenacity epoxy modified polyurethane composite is 30min,
Compared to common high hardness polyurethane material, gel time is significantly increased, and operable time extends, and is suitable to prepare large-scale and structure
Complicated product.Material properties test result see table 1, and as can be seen from Table 1, the material hardness of preparation is up to shore D70,
Impact property is superior.
Table 1：Material properties test result
| Detection corner | Test result |
| Hardness (shore D) | 70 |
| Tensile strength (MPa) | 40 |
| Elongation at break (%) | 15 |
| Bending strength (MPa) | 50 |
| Impact strength (KJ/m2) | 110 |
Tensile strength >=the 35MPa of the epoxy modified polyurethane composite of the present embodiment, elongation at break >=12%, bending is strong
Degree >=40MPa, impact strength >=100KJ/m2.
Embodiment 2：
A kind of high rigidity epoxy modified polyurethane composite of the present invention, Shore D hardness >=70 of this composite, this ring
Oxygen modified polyurethane composite is by component A and B component being added in the closed container of vacuum-pumping using prepolymer method
Prepare after carrying out hybrid reaction；Component A is the mixture of isocyanate terminated performed polymer and epoxy resin；B component is chain extension
Agent and the mixture of catalyst.
The preparation method of the above-mentioned high rigidity epoxy modified polyurethane composite of the present embodiment, specifically includes following steps：
1. prepare isocyanate terminated performed polymer
Isocyanate terminated performed polymer is prepared using PEPA and polyisocyanates polymerisation, specifically includes following steps：With
Mass fraction meter, the polyethylene glycol adipate glycol (PEA, equivalent 500, degree of functionality 2) of 60.5g is added reactor,
Keep vacuum at 115 DEG C under the conditions of 0.09～0.1MPa, be dehydrated 2.5h；Then cool to 50 DEG C, add 39.5g
Polyisocyanates, polyisocyanates select toluene di-isocyanate(TDI) (TDI, NCO content 48.3%), constant temperature under the conditions of 82 DEG C
Reaction 2h, cooling discharging, prepared nco value is 14% isocyanate terminated performed polymer.
2. prepare component A
Component A mixes acquisition by above-mentioned prepared isocyanate terminated performed polymer with epoxy resin, specifically under the conditions of 60 DEG C,
(epoxy resin selects E-44, epoxide number to add 35g epoxy resin in the isocyanate terminated performed polymer of above-mentioned prepared 100g
0.44mol/100g) mixing obtains afterwards.According to epoxy addition and epoxide number, calculating epoxy radicals molal quantity is 0.154mol.
3. prepare B component
The preparation of B component is under the conditions of 70 DEG C, and by 6.03g diglycol, (degree of functionality 2, equivalent 53 molar fraction take
70%), 2.20g trimethylolpropane (TMP, degree of functionality 3, equivalent 45, molar fraction take 30%) and 0.08g catalyst
(selecting 2-ethyl-4-methylimidazole) is sufficiently mixed rear discharging, altogether 8.23g.
The quality of required chain extender calculates in such a way：
Diglycol quality=[(14/42) × 0.95-0.154] × 0.7 × 53=6.03g；
TMP mass=[(14/42) × 0.95-0.154] × 0.3 × 45=2.20g.
4.A component is mixed with B component
It is separately heated to 65 DEG C by weighing good above-mentioned 135gA component with 8.23g B component raw material, be added to the close of vacuum-pumping
Close mixing in container, vacuumize 1～3min while stirring, take out after bubble purifies, be poured in mould, under the conditions of 90 DEG C
The demoulding after solidification 2h, then under the conditions of 110 DEG C, after cure 10h, prepared high rigidity, high-toughness polyurethane epoxy composite material
Material.
Gel time according to the high rigidity of above-described embodiment preparation, high tenacity epoxy modified polyurethane composite is 25min,
Compared to common high hardness polyurethane material, gel time is significantly increased, and operable time extends, and is suitable to prepare large-scale and structure
Complicated product.Material properties test result see table 2, and as can be seen from Table 2, the material hardness of preparation is up to shore D73,
Impact property is superior.
Table 2：Material properties test result
| Detection corner | Test result |
| Hardness (shore D) | 73 |
| Tensile strength (MPa) | 45 |
| Elongation at break (%) | 20 |
| Bending strength (MPa) | 52 |
| Impact strength (KJ/m2) | 105 |
Tensile strength >=the 35MPa of the epoxy modified polyurethane composite of the present embodiment, elongation at break >=12%, bending is strong
Degree >=40MPa, impact strength >=100KJ/m2.
Embodiment 3：
A kind of high rigidity epoxy modified polyurethane composite of the present invention, Shore D hardness >=70 of this composite, this ring
Oxygen modified polyurethane composite is by component A and B component being added in the closed container of vacuum-pumping using prepolymer method
Prepare after carrying out hybrid reaction；Component A is the mixture of isocyanate terminated performed polymer and epoxy resin；B component is chain extension
Agent and the mixture of catalyst.
The preparation method of the above-mentioned high rigidity epoxy modified polyurethane composite of the present embodiment, specifically includes following steps：
1. prepare isocyanate terminated performed polymer
Isocyanate terminated performed polymer is prepared using PPG and polyisocyanates polymerisation, specifically includes following steps：With
Mass fraction meter, the PTMG (PTMG, equivalent 500, degree of functionality 2) of 44.28g is added reactor,
Keep vacuum at 105 DEG C under the conditions of 0.09～0.1MPa, be dehydrated 2.5h；Then cool to 55 DEG C, add 55.72g
Polyisocyanates, polyisocyanates select diphenyl methane -4,4 '-diisocyanate (NCO content 33.6%), 85 DEG C of conditions
Lower isothermal reaction 2h, cooling discharging, prepared nco value is 15% isocyanate terminated performed polymer.
2. prepare component A
Component A mixes acquisition by above-mentioned prepared isocyanate terminated performed polymer with epoxy resin, specifically under the conditions of 50 DEG C,
(epoxy resin selects E-35, epoxide number to add 30g epoxy resin in the isocyanate terminated performed polymer of above-mentioned prepared 100g
0.35mol/100g) mixing obtains afterwards.According to epoxy addition and epoxide number, calculating epoxy radicals molal quantity is 0.105mol.
3. prepare B component
The preparation of B component is under the conditions of 70 DEG C, and by 8.29g 1, (equivalent 59, degree of functionality 2, molar fraction take 6- hexylene glycol
60%), 2.91g glycerine (degree of functionality 3, equivalent 31, molar fraction take 40%) and 0.05g catalyst are (from 2- methyl
Imidazoles) it is sufficiently mixed rear discharging, 11.20g altogether.
The quality of required chain extender calculates in such a way：
1,6 hexylene glycol quality=[(15/42) × 0.95-0.105] × 0.6 × 59=8.29g；
Glycerine quality=[(15/42) × 0.95-0.105] × 0.4 × 31=2.91g.
4.A component is mixed with B component
It is separately heated to 60 DEG C by weighing good above-mentioned 130gA component with 11.20g B component raw material, be added to the close of vacuum-pumping
Close mixing in container, vacuumize 1～3min while stirring, take out after bubble purifies, be poured in mould, under the conditions of 80 DEG C
The demoulding after solidification 1h, then under the conditions of 120 DEG C, after cure 10h, prepared high rigidity, high-toughness polyurethane epoxy composite material
Material.
Gel time according to the high rigidity of above-described embodiment preparation, high-toughness polyurethane epoxy composite material is 22min, compared to
Common high hardness polyurethane material, gel time is significantly increased, and operable time extends, and is suitable to prepare large-scale or complex structure system
Part.Material properties test result see table 3, and as can be seen from Table 3, the material hardness of preparation is up to shore D75, impact
Can be superior.
Table 3：Material properties test result
| Detection corner | Test result |
| Hardness (shore D) | 75 |
| Tensile strength (MPa) | 38 |
| Elongation at break (%) | 22 |
| Bending strength (MPa) | 45 |
| Impact strength (KJ/m2) | 108 |
Tensile strength >=the 35MPa of the epoxy modified polyurethane composite of the present embodiment, elongation at break >=12%, bending is strong
Degree >=40MPa, impact strength >=100KJ/m2.
Above example shows, the preparation method of the present invention can be obtained high rigidity epoxy modified polyurethane composite, and adopts
With the catalyst of the present invention, very exothermic does not occur in course of reaction, compound gel time is up to 30min.With above-mentioned enforcement
As a example example 1, it is 30g in epoxy resin addition, when accounting for total amount about 22%, material hardness value, up to Shao's D70 degree, is compared not
Add the situation of epoxy resin, hardness number improves 20.Further, since epoxy resin is cheap and easy to get, and using pure polyurethane resin
The high hardness material of preparation is compared, and cost can also decrease.
Claims (10)
1. a kind of high rigidity epoxy modified polyurethane composite is it is characterised in that described epoxy modified polyurethane composite is
Carry out preparing after hybrid reaction by component A and B component being added in the closed container of vacuum-pumping using prepolymer method；
Described component A is the mixture of isocyanate terminated performed polymer and epoxy resin；So B component is the mixing of chain extender and catalyst
Thing.
2. high rigidity epoxy modified polyurethane composite according to claim 1 is it is characterised in that described epoxide modified
Shore D hardness >=70 of compound polyurethane material.
3. high rigidity epoxy modified polyurethane composite according to claim 1 and 2 is it is characterised in that described epoxy
Tensile strength >=the 35MPa of modified polyurethane composite, elongation at break >=12%, bending strength >=40MPa, impact strength
≥100KJ/m2.
4. a kind of preparation method of the high rigidity epoxy modified polyurethane composite as any one of claims 1 to 3,
Comprise the following steps：
Weigh 130～140 parts of component A, 2.4～15.2 parts of B component, preheat respectively；Then by preheated component A and B
Component is added to mixing in the closed container of vacuum-pumping, carries out vacuum defoamation while stirring, takes out after bubble purifies, cast
To in corresponding mould, then carry out low-temperature setting, the demoulding, then heat sulfuration, prepared high rigidity epoxy modified polyurethane composite wood
Material；
Described component A is the mixture of isocyanate terminated performed polymer and epoxy resin；So B component is chain extender and catalyst
Mixture.
5. preparation method according to claim 4 is it is characterised in that the preparation of described component A includes：50 DEG C～
To in the isocyanate terminated performed polymer of 100 mass parts, under the conditions of 80 DEG C, add the epoxy resin of 30～40 mass parts, after fully mixing
Prepared component A.
6. preparation method according to claim 4 is it is characterised in that described isocyanate terminated performed polymer exists for nco value
Isocyanate terminated performed polymer between 13%～16%, described isocyanate terminated performed polymer is by PPG and/or PEPA
Prepare with after polyisocyanates polymerisation；Described epoxy resin includes E-54, E-51, E-44, E-42, E-35, E-31
One or more of mixture.
7. preparation method according to claim 6 is it is characterised in that described PPG is PTMG two
Alcohol, polypropylene oxide glycol, described PEPA include polybutylene glyool adipate, polycaprolactone glycol, gather oneself two
Sour glycol ester glycol, polyadipate ethylene glycol and 1,2-propylene glycol esterdiol, polyadipate diglycol esterdiol, polyadipate
One or more of -1,4- butyl glycol ester diol, polyadipate neopentyl glycol -1,6-HD esterdiol, PCDL
Mixture；
Described polyisocyanates includes diphenyl methane -4,4 '-diisocyanate, Carbodiimide-Modified MDI, MDI-50,
Toluene di-isocyanate(TDI), 3,3 '-dimethyl diphenyl diisocyanate, PPDI or hydrogenated diphenyl methane two isocyanic acid
Ester.
8. the preparation method according to any one of claim 4～7 is it is characterised in that described isocyanate terminated performed polymer
Preparation include：The PPG of 100 mass parts and/or PEPA are added reactor, in 100 DEG C～130 DEG C conditions
Lower holding vacuum, in 0.09～0.1MPa, is dehydrated；Then cool, add the polyisocyanates of 48～188 mass parts,
Isothermal reaction 2～3h under the conditions of 80 DEG C ± 5 DEG C, cooling discharging, isocyanate terminated performed polymer is obtained.
9. the preparation method according to any one of claim 4～7 is it is characterised in that the preparation of described B component includes：
Under the conditions of 50 DEG C～80 DEG C, after the catalyst of measure 2.4～15.2 parts of chain extender and 0.01～0.1 part is sufficiently mixed
Discharging；
Described chain extender is mixed to prepare with three-functionality-degree chain extender using two degrees of functionality of water content≤0.05%；Described two degrees of functionality expand
The molar fraction that chain agent consumption accounts for chain extender total amount is 50%～80%；Described three-functionality-degree chain extender consumption accounts for chain extender total amount
Molar fraction is 20%～50%；Described two degree of functionality chain extenders include ethylene glycol, propane diols, butanediol, hexylene glycol, a contracting
At least one in diethylene glycol, methyl propanediol, Isosorbide-5-Nitrae-cyclohexandiol, neopentyl glycol；Described three-functionality-degree chain extender includes
At least one in glycerine, trimethylolpropane；
Described catalyst select 2-methylimidazole, 2-ethyl-4-methylimidazole, 2- phenylimidazole, 1- benzyl -2-methylimidazole,
One of 1- 1-cyanoethyl-2-methylimidazole.
10. the preparation method according to any one of claim 4～7 is it is characterised in that described component A and B component
Preheating temperature controls at 50 DEG C～80 DEG C；The time control of described vacuum defoamation is in 1～3min；The temperature of described low-temperature setting is
80 DEG C～100 DEG C, hardening time is 1～2h；Described plus heat-vulcanized temperature is 100 DEG C～120 DEG C, cure time is 10～
16h.
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