CN107383320A - The preparation method of epoxy resin modification shape memory polyurethane - Google Patents
The preparation method of epoxy resin modification shape memory polyurethane Download PDFInfo
- Publication number
- CN107383320A CN107383320A CN201710760010.9A CN201710760010A CN107383320A CN 107383320 A CN107383320 A CN 107383320A CN 201710760010 A CN201710760010 A CN 201710760010A CN 107383320 A CN107383320 A CN 107383320A
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- CN
- China
- Prior art keywords
- epoxy resin
- shape memory
- memory polyurethane
- calking
- cement pavement
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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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
- C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
-
- 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
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
-
- 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
- C08G2280/00—Compositions for creating shape memory
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Road Paving Structures (AREA)
Abstract
The present invention provides a kind of preparation method of epoxy resin modification shape memory polyurethane, belongs to the new caulking material technical field of cement pavement, solves small conventional polyurethanes restoring force, low intensity, crack resistance is poor, lacks the problems such as shape memory function.The present invention will first be dehydrated polyadipate 1; 4 butyl glycol ester diols and 2; 4 toluene-2,4-diisocyanates react 2 hours synthesis shape memory polyurethane performed polymers in the case where 80 DEG C of nitrogen are protected; then different addition quantity epoxy resin is added at 70 DEG C; it is added dropwise 1; 4 butanediols carry out chain extension; quick stirring is reacted after 30 minutes obtains modified composite material, and the optimum mix amount of epoxy resin is determined finally by test synthesis such as phase transition temperature, Dynamic thermo-mechanical property, FTIR spectrum, mechanical property, shape-memory properties.Epoxy resin modification shape memory polyurethane prepared by the present invention can be used as cement pavement calking, can improve the performance of calking, pavement destruction be reduced, so as to improve the service quality of cement pavement.
Description
Technical field
The present invention is a kind of preparation method of epoxy resin modification shape memory polyurethane, belongs to the new filleting of cement pavement
Field of material technology.
Background technology
With the fast development of Highway Cause, cement pavement is widely used in weight with the advantages that its intensity is high, stability is good
On the more road of carrier vehicle.In order to effectively control because deformation caused by the reasons such as temperature, load damages cement road surface plate, generally
Various seams (including expansion joint (E.J.), contracting seam etc.) are set every a segment distance on pavement structure.But seam is that cement pavement is most weak
Link, calking failure be the main reason for causing destruction of joint.
China's cement pavement calking development is slower, and conventional calking mainly has pitch class, clay class, rubber
Class, resinae and prefabrication type caulking strip, sealing strip etc..Application practice shows that early damage easily occurs in above-mentioned calking；Can not
Meet the requirement that concrete slab expands with heat and contract with cold, high temperature easily trickles, and low temperature easily ftractures, and is easily disengaged with concrete slab；
It is easily destroyed under Repeated Loading, easy aging etc. under natural environmental condition, so as to cause the destruction of cement pavement, influences
Usage capability of road.In order to improve the service life of cement pavement, many road researchers carry out the research and development or of new materials
There is the modification of calking.
With the rise of high polymer material, researchers are also applied it in road engineering.Wherein, polyurethane is because of its tool
Have the advantages that good toughness, wearability, easy preparative, price are relatively low as one of important calking, but polyurethane caulking
Material still can not fundamentally solve to perceive the problems such as blunt to environmental change.Research shows, due to the selection of raw material, mixing ratio
The difference of example, the polyurethane of synthesis generally have different performances, and specific polyurethane has SME.When higher than phase
Material produces deformation under external force during transition temperature, and temperature declines deformation and fixed, when temperature rises to phase in version temperature again
When on degree, material can return back to its original-shape, and this SME can make calking actively adapt to joint gap
Telescopic variation.
However, shape memory polyurethane limits there is also the shortcomings of restoring force is small, low intensity, crack resistance poor, easy to aging
Its application as engineering material.There is research by mixing CNT, the shape of graphene raising shape memory polyurethane is consolidated
Determine rate, shape recovery rate, mechanical performance, also have research by mixing fiber, nano particle improves its performance.In addition,
There is researcher that thermoplastic polymer, epoxy resin, silicones etc. are used for into modified polyurethane.The asphalt mixtures modified by epoxy resin in numerous reinforcing materials
Fat has high intensity, highly corrosion resistant and preferable heat endurance, is one of most important thermosetting modification agent.Research shows,
Inierpeneirating network structure is formed by epoxy resin modification polyurethane, the performances such as mechanics, the heat endurance of material can be improved.But
Epoxy resin modification polyurethane is not studied according to requirement of engineering at present, and there is also some problems needs to solve, such as compound
The shape memory transition temperature of material, SME, mechanical property etc. are unsatisfactory for the requirement of practical engineering application.
Therefore, the present invention adjusts epoxy resin modification shape memory polyurethane for cement pavement actual application environment
Shape memory transition temperature, research epoxy resin content is to shape memory transition temperature, SME, mechanical property etc.
Influence, to provide a kind of new method to be modified shape memory polyurethane, improve it and adapt to cement pavement seam crossing working environment
Ability, improve its service quality, so as to extend the service life of cement pavement seam.
The content of the invention
(1) technical problem
It is an object of the invention to provide a kind of epoxy resin modification shape memory for adapting to cement pavement seam condition of work
The preparation method of polyurethane caulking material, this method have according to cement pavement seam crossing condition of work with reference to epoxy resin, polyurethane
Some special performances carries out Material composition design, determines prepared by rational proportion, so as to solve conventional polyurethanes restoring force it is small,
Low intensity, crack resistance be poor, it is easy to aging, lack the problems such as shape memory function, calking is better conformed to cement pavement seam crossing
Condition of work, calking durability, retractility, anti-embeddability are improved, avoids the occurrence of early damage.
(2) technical scheme
In view of traditional asphalt base, polymer matrix cement pavement calking are blunt to environmental change perception, easy generation extruding,
Cracking caused by stretching etc. or damage, it is impossible to meet the requirement such as the displacement of cement pavement seam crossing, mechanics, durability, root of the present invention
According to the condition of work of calking, the polyurethane with shape-memory properties is chosen as matrix material, it is contemplated that shape memory gathers
The shortcomings that urethane, its mechanical property is improved using epoxy resin modification, proposes a kind of suitable cement pavement seam condition of work
The preparation method of epoxy resin modification shape memory polyurethane calking, so as to improve the performance of calking.Skill of the present invention
Art scheme is as follows：First, the raw material for preparing shape memory polyurethane matrix are chosen according to cement pavement seam crossing temperature,
Shape memory polyurethane performed polymer is first synthesized by solution prepolymer method, then the epoxy of different addition quantity is added into prepolymer solution
Resin, and BDO is added dropwise and carries out chain extension, such as Fig. 1, obtain epoxy resin modification shape memory polyurethane composite wood
Material, and phase transition temperature, Dynamic thermo-mechanical property, FTIR spectrum, mechanical property, shape-memory properties etc. are carried out to it
Test, comprehensive every test result, the optimum mix amount of epoxy resin is determined, so as to improve the performance of calking, improves water
Mud pavement durability and service quality.
(3) beneficial effect
Highway Cause development is increasingly flourishing, and road maintenance increasingly attracts attention, the performance improvement of cement pavement calking
Also gradually it is taken seriously.Currently used cement pavement calking easily occurs under the repeated action of temperature change and traffic load
Extrude, come off, ftracture, pollute the problems such as road surface.The present invention is using application is relatively broad, price is relatively low, is adapted to largely use workmanship
The shape memory polyurethane of journey calking can be such that calking realizes from deforming, actively adapt to cement pavement seam as matrix
Change width, it can be stretched well with cement road surface plate.Changed in addition, adding appropriate epoxy resin in the base
Property, because epoxy resin has the advantages that intensity high, corrosion resistance and heat endurance are good, can improve calking mechanical property and
Thermal property.The composite that epoxy resin modification shape memory polyurethane is prepared can work with cement pavement seam crossing
Environment temperature field matches, and better adapts to pavement joint condition of work, reduces pavement destruction, to improve Road Service Life,
Maintenance cost is reduced to have great importance.
Brief description of the drawings
Fig. 1 epoxy resin modifications shape memory polyurethane prepares Experimental equipment
1- agitators；2- condenser pipes；3- iron stands；4- four-hole boiling flasks；5- heating mantles；6- water seals
Embodiment
It is embedding that the present invention provides a kind of epoxy resin modification shape memory polyurethane for adapting to cement pavement seam condition of work
The preparation method of sewing, specific implementation step are as follows：
(1) by the polyadipate of certain amount of calculation-BDO esterdiol put into equipped with thermometer, mixer,
In the 250ml of gas import and export four-hole boiling flask, vacuum dehydration 1.5 hours at 120 DEG C, vacuum is all the time during experiment
More than 0.095Mpa；
(2) when temperature is down to 80 DEG C, 2, the 4- toluene-2,4-diisocyanates of certain amount of calculation are added by proportioning, are protected in nitrogen
Under shield, temperature stabilization reacts 2 hours at 80 DEG C, and shape memory polyurethane performed polymer is made；
(3) when temperature further drops to 70 DEG C, the epoxy resin of certain amount of calculation is added into obtained performed polymer,
And the chain extender BDO of certain amount of calculation is added dropwise, quick stirring makes it react completely in 30 minutes；
(4) mixed solution is injected in Teflon mould at once after question response terminates, it is naturally cooled to room temperature,
And solidify 1 hour, shape memory polyurethane composite material sample is made after the demoulding, various performance tests are carried out after placing one week；
(5) verify whether epoxy resin is successfully accessed shape memory polyurethane master according to FTIR spectrum analysis result
In chain, shape memory polyurethane phase transition temperature is influenceed using differential scanning calorimetry difference epoxy resin addition,
And using the thermodynamic performance of dynamic thermomechanical analysis apparatus test epoxy resin modification shape memory polyurethane；
(6) comprehensive every test result inquires into Different adding amount epoxy resin to shape memory polyurethane mechanical property and shape
The influence of shape memory effect, epoxy resin optimum addition is determined, fit epoxy resin modification shape memory polyurethane calking
Cement pavement seam condition of work is answered, improves calking durability, extends cement pavement service life.
Claims (1)
- A kind of 1. preparation side of the epoxy resin modification shape memory polyurethane calking of suitable cement pavement seam condition of work Method, it is characterised in that this method comprises the following steps that：(1) polyadipate of certain amount of calculation-BDO esterdiol is put into equipped with thermometer, mixer, gas In the 250ml of import and export four-hole boiling flask, vacuum dehydration 1.5 hours at 120 DEG C, vacuum is consistently greater than during experiment 0.095Mpa；(2) when temperature is down to 80 DEG C, 2, the 4- toluene-2,4-diisocyanates of certain amount of calculation are added by proportioning, are protected in nitrogen Under, temperature stabilization reacts 2 hours at 80 DEG C, and shape memory polyurethane performed polymer is made；(3) when temperature further drops to 70 DEG C, the epoxy resin of certain amount of calculation is added into obtained performed polymer, and by The chain extender BDO of certain amount of calculation is added dropwise to, quick stirring makes it react completely in 30 minutes；(4) mixed solution is injected in Teflon mould at once after question response terminates, it is naturally cooled to room temperature, and it is solid Change 1 hour, shape memory polyurethane composite material sample is made after the demoulding, various performance tests are carried out after placing one week；(5) verify whether epoxy resin is successfully accessed shape memory polyurethane main chain according to FTIR spectrum analysis result In, shape memory polyurethane phase transition temperature is influenceed using differential scanning calorimetry difference epoxy resin addition, and Using the thermodynamic performance of dynamic thermomechanical analysis apparatus test epoxy resin modification shape memory polyurethane；(6) comprehensive every test result inquires into Different adding amount epoxy resin and shape memory polyurethane mechanical property and shape is remembered Recall the influence of effect, determine epoxy resin optimum addition, epoxy resin modification shape memory polyurethane calking is adapted to water Mud pavement joint condition of work, calking durability is improved, extend cement pavement service life.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108192548A (en) * | 2017-12-29 | 2018-06-22 | 广东铁科灌浆科技有限公司 | Permanent seal cooling epoxy resin caulking material and preparation method thereof |
| CN110437402A (en) * | 2019-08-09 | 2019-11-12 | 中国科学院兰州化学物理研究所 | A kind of preparation method of the interpenetrating net polymer with shape-memory properties |
| CN110683791A (en) * | 2019-09-18 | 2020-01-14 | 长安大学 | Super-silent pavement paving material and application |
| CN116063859A (en) * | 2023-03-07 | 2023-05-05 | 内蒙古大学 | New material for repairing pavement cracks in high-altitude cold areas and preparation method thereof |
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|---|---|---|---|---|
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| CN110683791A (en) * | 2019-09-18 | 2020-01-14 | 长安大学 | Super-silent pavement paving material and application |
| CN116063859A (en) * | 2023-03-07 | 2023-05-05 | 内蒙古大学 | New material for repairing pavement cracks in high-altitude cold areas and preparation method thereof |
| CN116063859B (en) * | 2023-03-07 | 2023-06-06 | 内蒙古大学 | Material for repairing pavement cracks in high-altitude cold areas and preparation method thereof |
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