CN102604368B - NCO replaced crosslinking cured joint filling material for concrete pavement - Google Patents
NCO replaced crosslinking cured joint filling material for concrete pavement Download PDFInfo
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Abstract
The invention relates to crosslinking joint filling glue for a concrete pavement, in which the active group -NOC of polyurethane is replaced. The joint filling glue is composed of a component A, a component B and an amine accelerating agent; when the joint sealing glue is need, the component A and the component B are taken according to a mass ratio of 1:1-2, simultaneously the amine accelerating agent accounting for 1.0%-2% of the mass of the component B is added, and the three materials are mixed and reacted to prepare the joint filling glue; the component A is a novel polyurethane prepolymer which is prepared by polymerizing polyether polyol, isocyanate, hydroxyl terminal organic silicon, a hyperbranched polymer with an esterifiable tail end part and a catalytic agent; and the componentB is formed by mixing the catalytic agent and multiple stuffing. The joint filling glue has the characteristics of good binding property, high elasticity, anti-fatigue and the like while overcoming the hydrophobic problem occurring when the traditional joint filling glue is used for field operation and the using problem of a carcinogenic crosslinking agent MOCA, has a long quality guarantee period and can solve the problem very well that the schedule of the joint filling operation of the concrete pavement is affected due to uncertain factors such as weather.
Description
Technical field
The present invention relates to the cement pavement pointing, particularly a kind of cement pavement pointing of the NCO of replacement crosslinking curing.
Background technology
At present at the most frequently used cement pavement gap-filling glue of China, based on polyurethane filling material, it is with its excellent characteristic, as watertight, airtight effect, flexible, cohesiveness and durable, weathering resistance, can stand for a long time to stretch, compress and vibration, cohesive force is strong, can stand seam crossing expands with heat and contract with cold and stretches repeatedly, compresses and be not destroyed and advantage such as easy construction, be widely used in cement concrete pavement, the quality of cement concrete pavement is improved, and service life of road surface is effectively prolonged simultaneously.
Polyurethane filling material is to be polymerized by isocyanic ester and polyether glycol, and two kinds of single component and two-packs are arranged usually.The polyurethane molecular chain is the segmented copolymer of the rigid chain segment combination that provides of the soft segment that provided by polyether glycol and isocyanic ester.Contain in the molecular structure of polyurethane filling material-NCO and-strong polar group such as OH, reaction can form tough elastic bonding layer after solidifying.These constructional features make polyurethane filling material have good elasticity and high adhesive property, and have characteristics such as oil resistant, wear-resisting, vibration resistance, antifatigue, high-low temperature resistant.Existing organic silicon modified polyurethane gap-filling glue is by introducing the method for organosilicon segment in molecule, it is poor that the introducing of Si has solved traditional polyurethane filling material weathering resistance, under long-term solar radiation, efflorescence flavescence easily, the shortcoming that obviously shorten work-ing life.
But, be traditional base polyurethane prepolymer for use as or organic-silicon-modified after base polyurethane prepolymer for use as all be by-NCO is crosslinked, and-the as easy as rolling off a log and active hydrogen reaction of NCO, when having water to exist, this end isocyanato base polyurethane prepolymer for use as can solidify and discharges carbon dioxide, glue-line is bubbled cause defective, become the work-ing life that influences polyurethane filling material, especially influence a fatal problem of moist pavement constructions such as greasy weather rainy day.In addition, isocyanate terminated polyurethane sealant uses the two Ortho-Chloro anilines of MOCA(methyne) as linking agent, though the solidification effect of MOCA is very good, MOCA is considered to human body is had the linking agent of carcinogenic danger.
At present, developed country is competitively developing waterproof urethane sealing material on the one hand both at home and abroad; Also be devoted to produce novel crosslinker on the other hand, attempt to replace MOCA.Thereby very be necessary to research and develop a kind of novel MOCA that do not need and make linking agent, substitute simultaneously tradition by-this water funk group of NCO is crosslinked, low toxicity, inexpensive, environmental protection, long urethane sealing material of life-span.
Hyperbranched polymer has comparatively complete tree crown structure, space structure presents sphere, the surface has a large amount of active function groups, this special structure has been given its high reaction activity, characteristics such as low viscosity, thus thereby can be by modification obtains the modified ultra-branching polymkeric substance of differential responses demand to the hyperbranched polymer functional end-group.Hyperbranched polymer shows huge using value at numerous areas such as coating, tackiness agent, auxiliary rheological agents and supramolecular chemistry, nanosecond science and technology, biomaterial, photoelectric material, medicine deliveries at present.
Summary of the invention
In order to solve the water funk drawback of above tradition end isocyanato base polyurethane prepolymer for use as, the invention provides a kind of water funk problem when having overcome the construction of traditional gap-filling glue, have excellent high temperature resistant, anti-immersion oil, erosion resistant characteristic, and the cement pavement pointing of fine anti-embedding degree and elastic restoration ratio is arranged.
The present invention realizes by the following method:
A kind of cement pavement gap-filling glue of the NCO of replacement crosslinking curing is made up of first component, second component and amine type accelerator,
Described first component obtains base polyurethane prepolymer for use as by the copolymerization under the effect of catalyzer Benzoyl chloride of polyether glycol, terminal hydroxy group organosilicon and isocyanic ester, obtain with olefin(e) acid partial esterification or the amidated hyperbranched polymer polymerization of part with end then, the end of described hyperbranched polymer is hydroxyl or amido;
Described second component is mixed by peroxide catalyst and filler,
Wherein first component and second constituent mass are than being 1:1～2, and amine type accelerator is 1.0%～2.0% of second constituent mass;
Terminal hyperbranched polymer with the olefin(e) acid partial esterification, C-terminal is 1:5～11 with the number ratio of ester group end,
Terminal with the amidated hyperbranched polymer of olefin(e) acid part, the amido end is 1:5～11 with the number ratio of amide group end.
Described cement pavement gap-filling glue, polyether glycol, isocyanic ester, terminal hydroxy group organosilicon, end are 10:2～3:1～3:6～10 with the weight ratio of the hyperbranched polymer of olefin(e) acid partial esterification in the first component.
Described cement pavement gap-filling glue, the weight ratio of catalyzer and filler is 1:20～40 in the second component, filler is more than one in talcum powder, light calcium carbonate, aerosil, calcium oxide, clorafin, UV light absorber, the pigment.
Described cement pavement gap-filling glue, peroxide catalyst are benzoyl peroxide, dibenzoyl peroxide or dilauroyl peroxide.
Described cement pavement gap-filling glue, the hydroxyl value of polyether glycol are 30～70mgKOH/g, and described terminal hydroxy group polymerizable organosilicon degree is 5～10, and described isocyanic ester is polyisocyanates.
Described cement pavement gap-filling glue, superbrnaching end-hydroxy polymkeric substance hydroxyl value is 19～46mgKOH/g.
Described cement pavement gap-filling glue, amine type accelerator are N, and the N-dimethyl is to aniline, N, accelerine or N, N-Diethyl Aniline.
Described cement pavement gap-filling glue, hyperbranched polymer prepares by following any method:
A, the reaction of 30.022g Succinic anhydried, 39.952 g diisopropanolamine (DIPA) is obtained AB
2The type monomer adds 1.916 g TriMethylolPropane(TMP)s as core molecule, adds the reaction of 0.3 g tosic acid and obtains the superbrnaching end-hydroxy polymkeric substance;
B, with 104 mL divinyl triamines, at N
2Protection adds 86 mL methyl acrylates down, and reaction 4 h obtain AB under the normal temperature
2The type monomer is warming up to 150 ℃ of decompression reaction 4 h then, obtains amine-terminated hyperbranced compound.
Described cement pavement gap-filling glue, the preparation technology of base polyurethane prepolymer for use as is as follows:
With polyether glycol, terminal hydroxy group organosilicon, add reaction vessel, under-0.092MP vacuum tightness, 90 ℃ of temperature are dehydration anhydrous come out on condenser down, is cooled to 50 ℃, at N
2Under protection and the whipped state, drip TDI, dropwise in 30min, be warming up to 80～82 ℃ then, polymerization under atmospheric pressure reacted 2 hours, and under the condition of 80～82 ℃ and vacuum tightness-0.092MP, decompression dehydration 2～3 hours is at N afterwards
2Protection makes system recover normal pressure down, is cooled to 70～75 ℃.
Described cement pavement gap-filling glue, the hyperbranched polymer polymerization process of base polyurethane prepolymer for use as and terminal portions esterification is as follows:
Get terminal hyperbranched polymer with the olefin(e) acid partial esterification, dissolving is at N
2Protection drips in base polyurethane prepolymer for use as down, drips off at 0.5～1 hour, and 70～75 ℃ of polymerization under atmospheric pressure reactions 4～6 hours, the desolventizing that dewaters then obtained the first component.Cement pavement gap-filling glue of the present invention, its principle is according to being:
Existing industrial production urethane gap-filling glue generally adopts prepolymer method, adopt the reaction of isocyanic ester and polyether glycol, had-base polyurethane prepolymer for use as of NCO end-blocking, but-NCO very easily and active hydrogen reaction, make cement highway joint filling operation just be difficult to carry out at rainy weather.Cement pavement gap-filling glue of the present invention is intended to usefulness-C=C and substitutes original crosslinked group-NCO as crosslinked group, but a spot of-C=C can not reach desirable cross-linking effect, there is the hyperbranched polymer of terminal special groups to increase-quantity of C=C by adding so, and make it reach suitable polymerization temperature and the time by the introducing of redox system, it is a good idea, has very big novelty, thereby expectation fundamentally solves the water funk drawback of tradition end isocyanato base polyurethane prepolymer for use as, reaches the purpose of structures shape character.
At first by regulating polyether glycol, the organosilyl kind of isocyanic ester and terminal hydroxy group and consumption, obtain-the different base polyurethane prepolymer for use as of NCO content, utilize then in this hyperbranched polymer end-in OH or amido and the base polyurethane prepolymer for use as-the NCO radical reaction, consumption by the control hyperbranched polymer makes in the base polyurethane prepolymer for use as-and NCO group complete reaction disappears, thereby obtain a kind of new polyurethane performed polymer that contains a large amount of two key end-blockings, this new polyurethane performed polymer in use adopts the redox system be made up of strong oxidizer and tertiary amines promotor to cause self-vulcanizing, thereby has solved traditional end isocyanato polyurethane sealant water funk problem and use problem of carcinogenic linking agent MOCA in construction.
Some special propertys of utilizing hyperbranched polymer to follow traditional linear macromolecule to compare to have, the molecular structure of the 3 D stereo shape that it is unique make molecular chain not have prehensile and no crystallinity.Its solubility property is good, and viscosity is low, when molecular weight increases or concentration when improving, still can keep lower viscosity, thereby and the terminal active group that has One's name is legion can be used for modification and introduce the group of needs.Its building-up process is simple relatively, does not need the separation of multistep to purify, and preparation is simple, and production cost is lower, is applicable to large-scale industrial production.The present invention proposes to contain in a large number-hyperbranched polymer of C=C and a small amount of-OH or amido with a kind of end, by this hyperbranched polymer end-in OH or amido and the base polyurethane prepolymer for use as-the NCO reaction, thereby obtain a kind of new polyurethane performed polymer that contains a large amount of two key end-blockings.In this new polyurethane performed polymer and the process that the second component is mixed, under the initiation of redox agent, cause by free radical reaction that two keys are crosslinked to obtain having the cancellated polymer elastomer in space.
Cement pavement of the present invention adopts following method preparation with pointing:
(1) preparation of first component
1) preparation of hyperbranched polymer
The hyperbranched polymer that uses among the present invention, end contains in a large number-C=C and a small amount of-OH or amido, and hyperbranched polymer is in order to introduce needs-C=C group, therefore, as long as can reach the hyperbranched polymer of this purpose, can use in the present invention.Because the hyperbranched polymer kind is many, can not enumerate one by one at this, but used hyperbranched polymer all should have or similar following structural formula:
R wherein
1, R
2Structural formula is:
R
1：
R
2：
Since used olefin(e) acid kind difference in the esterification, R
2The type end structure is difference to some extent, but all be to have-structure of C=C, is example with the carbon-carbon double bond end behind the acroleic acid esterification only herein.
R
1Type end and R
2The terminal number of type is than being that 1:5 ~ 11 are excellent, if R
1Type end and R
2The terminal number of type is than 1:23, and it is too big that the reaction of NCO and OH or amido is subjected to space steric effect, can influence the carrying out of reaction.This hyperbranched polymer hydroxyl value measured value is at 19～46mgKOH/g, and viscosity is 8.3 ~ 23.6 mPaS.Structure irregularity degree height when hyperbranched polymer is synthetic, and the problem that moves of esterification balance, the hydroxyl value of hyperbranched polymer should be a value range can using production, viscosity also is like this.
The preparation of above-mentioned hyperbranched polymer, any method that can adopt those skilled in the art to realize, as long as it is just passable to synthesize the polymkeric substance of said structure formula, the present invention is the following synthetic method of concrete use in preparation process, and use therein material proportion, processing parameter all are that this area is commonly used.
Because the hyperbranched polymer kind is many, can not enumerate one by one at this.Now with the example that is prepared as of the superbrnaching end-hydroxy polyesteramide of terminal portions esterification, concrete synthetic method is as follows:
1. utilize acid anhydrides under lower temperature can with diisopropanolamine (DIPA) in-NH-carries out amidate action.Diisopropanolamine (DIPA) is dissolved among the DMAc (N,N-DIMETHYLACETAMIDE), pour in the there-necked flask that has magnetic stirring apparatus after the dissolving fully, again Succinic anhydried is dissolved with DMAc, then it is slowly dripped in the there-necked flask and stir while dripping, in 1～3 hour, dropwise, then reacted at normal temperatures 3～6 hours, and obtained having the AB of a carboxyl and two hydroxyls
2The type monomer.Reaction equation is as follows:
2. in above-mentioned system, add toluene earlier as the band aqua, add core molecule TriMethylolPropane(TMP) and catalyzer tosic acid again, reflux is divided water, and insulation reaction 6～8 hours obtains the super-branched polyesteramide of terminal hydroxy group, and reaction equation is as follows:
3. drip olefin(e) acid in above-mentioned system, dropwised in 1～3 hour, the control temperature of reaction is at 90～120 ℃, and reflux water-dividing reacted 4～6 hours, and underpressure distillation desolventizing then and remaining olefin(e) acid obtain hyperbranched polymer.Reaction equation is as follows:
The hydroxyl value of having measured the hyperbranched polymer that is synthesized by employing acetic acid pyridine circumfluence method is 19～46mgKOH/g.From the observed value of hydroxyl value as can be seen, the terminal a large amount of hydroxyl of the hyperbranched polymer that is synthesized disappears.With the digital display viscometer viscosity of this hyperbranched type polymkeric substance is measured, the hyperbranched polymer viscosity of being synthesized is 8.3-23.6 mPaS, from observed value as can be seen, this hyperbranched polymer has lower viscosity, can in base polyurethane prepolymer for use as system good dispersion be arranged.
Step 3. in used olefin(e) acid can be vinylformic acid, butenoic acid and 2-methyl-unsaturated carboxylic acids such as 4-pentenoic acid, can realize the effect of terminal hydroxy group partial esterification, reach service requirements of the present invention, but consider space steric effect, preferred vinylformic acid.
Hyperbranched polymer also can be end amino superbranching polymkeric substance, for example prepares end amino superbranching polymkeric substance by divinyl triamine and methyl acrylate.
2)-preparation of the base polyurethane prepolymer for use as of NCO end-blocking
1. with the polyether glycol that measures, terminal hydroxy group organosilicon and Benzoyl chloride add in the reaction vessel of dry cleansing.
2. under the vacuum tightness about-0.092MP, open circulating condensing water, open stirring.The control temperature is about 90 ℃, and dehydration during substantially anhydrous come out, is cooled to 50 ℃ on condenser.
3. at N
2Protection is down opened stirring, slowly drips TDI in the material that finishes to above-mentioned dehydration; strict control temperature of reaction in case the generation of implode reaction dropwises, slowly is warming up to 80～82 ℃ then in 30min about 50 ℃; keep this temperature range, polymerization under atmospheric pressure reaction 2 hours.Close N
2Intake valve is opened vacuum system, the holding temperature scope under the condition about 80～82 ℃ and vacuum tightness-0.092MP, decompression dehydration 2～3 hours.Close vacuum system then, open N
2Intake valve is at N
2Protection makes system recover normal pressure down.
3) base polyurethane prepolymer for use as active group-NCO's substitutes
1. with 1) hyperbranched polymer that synthesized is dissolved among the DMAc through processed.
2. at N
2Protection down, strict control temperature of reaction is at 70～75 ℃, to 2) in the system that 3. the step reaction finishes, drip the hyperbranched polymer that synthesize, polymerization under atmospheric pressure reacted 4～6 hours.Then close N
2Intake valve, open vacuum system, the holding temperature scope about 80～82 ℃ and vacuum tightness-0.092MP, dehydration reaction 1～3 hour, then be warming up to about 110 ℃, continue underpressure distillation and removed solvent DMAc in 1～2 hour, dripless occurs to the condenser, returns to normal pressure gradually, close vacuum system, be cooled to 60 ℃, be discharged in plastics or the metal bucket container, obtain the first component.
(2) preparation of second component
With peroxide catalyst, talcum powder, in light calcium carbonate, aerosil, calcium oxide, clorafin, UV light absorber, the pigment more than one mix under certain temperature condition, then with the sufficient dispersed with stirring of homogenizer, grind repeatedly with three-roll grinder, the sealing deepfreeze is stand-by again.
Used peroxide catalyst can be superoxide such as benzoyl peroxide, dibenzoyl peroxide, dilauroyl peroxide, is preferably benzoyl peroxide.
(3) amine type accelerator deposits
N, accelerine (DMA) is deposited separately under lucifuge, cold condition.
Used amine type accelerator is N in the step (3), and the N-dimethyl is to aniline, N, accelerine or N, and tertiary amines promotor such as N-Diethyl Aniline are preferably N, accelerine (DMA).
(4) performance test of cement pavement gap-filling glue of the present invention
First component and second component are got material by the mass ratio of 1:1.5, add the N of second constituent mass 1.5% simultaneously, accelerine (DMA), high-speed stirring mixes, be applied in the various test mould therefors, self-vulcanizing obtains polyurethane filling material of the present invention, carries out performance test.Its surface drying time was at 4～8 hours, penetration degree is 2mm, and elastic restoration ratio is 82%, and tensile strength is 1.46MPa, aging back draft intensity is 1.18MPa, the maximum elongation rate is 930%, and aging back maximum elongation rate is 732%, and cohesive strength is 0.40MPa, aging back cohesive strength is 0.35MPa, combustion initiation temperature is 280 ℃, and 80 ℃ of * did not trickle in 168 hours, and-40 ℃ of * did not ftracture in 168 hours.The immersion oil test shows that polyurethane filling material mass loss rate of the present invention is 2.6%, volume change 3.2%.Cement pavement replaces because of the four seasons, the influence of temperature height, and cement sheeting can produce the cold drawn phenomenon of hot pressing to the slit.In order to verify the anti-fatigue performance of this gap-filling glue,-30 ℃ and 20 ℃ this gap-filling glue is carried out the cold drawn experiment of hot pressing, experimental results show that this pointing not only can carry out at 100% time, and behind hot pressing cold drawing operation repeatedly, still can satisfy displacement and surpass 50% requirement.These results show that this gap-filling glue has excellent high temperature resistant, anti-immersion oil, erosion resistant characteristic, and fine anti-embedding degree and elastic restoration ratio are arranged, and is a kind of good cement pavement pointing.
Beneficial effect of the present invention: when the crosslinked waterproof cement pavement pointing of the active group-NCO of this replacement urethane of the present invention water funk problem and MOCA linking agent when having overcome traditional gap-filling glue construction use problem, still characteristics such as advantages of good caking property, snappiness and antifatigue have been kept, it is a kind of long quality-guarantee period, can fine solution because uncertain factors such as weather influence the novel pointing of cement pavement joint filling job scheduling, have good market development prospect.
Embodiment
Below cement pavement of the present invention is described in more detail with pointing, its purpose is to illustrate design of the present invention and characteristics, can not limit protection scope of the present invention with this.All equivalences that spirit is done according to the present invention change or modify, and all should be encompassed within protection scope of the present invention.
Example 1
(1) takes by weighing 30.022g Succinic anhydried, 39.952 g diisopropanolamine (DIPA), at first diisopropanolamine (DIPA) is dissolved in 70 mLDMAc, pour into after the dissolving in the there-necked flask that has magnetic stirring apparatus, again Succinic anhydried is dissolved with 70 mLDMAc, then it is slowly dripped in the there-necked flask and stir while dripping, approximately dripped 1 hour, normal-temperature reaction 3 hours gets AB
2The type monomer.Add 60 mL toluene (toluene is the band aqua) earlier in above-mentioned system, add 1.916 g TriMethylolPropane(TMP)s as core molecule, add 0.3 g tosic acid, begin heating then, until boiling, having in the spherical condensation tube refluxes produces.After being incubated anti-7 h, in this system, slowly drip 15mL vinylformic acid, approximately dripped 1 hour, the control temperature of reaction is at 90～120 ℃, reflux water-dividing, reacted 4～6 hours, underpressure distillation desolventizing then and excessive vinylformic acid obtain the hyperbranched polymer that end contains small amount of hydroxyl groups and a large amount of-C=C.
(2) be 2000 with the 20g molecular weight, hydroxyl value is the 54-58mgKOH/g polyoxypropyleneglycol, and the 30g molecular weight is 3050, and hydroxyl value is 55-58mgKOH/g polyoxytrimethylene triol, the 15g polymerization degree is 5～7 terminal hydroxy group organosilicon, adds in the reaction vessel of dry cleansing.Under the vacuum tightness about-0.092MP, open circulating condensing water, open stirring.The control temperature is about 90 ℃, and dehydration during substantially anhydrous come out, is cooled to 50 ℃ on condenser.At N
2Protection is down opened stirring, slowly drips 10gTDI in the material that finishes to above-mentioned dehydration; strict control temperature of reaction in case the generation of implode reaction dropwises, slowly is warming up to 80～82 ℃ then in 30min about 50 ℃; keep this temperature range, polymerization under atmospheric pressure reaction 2 hours.Close N
2Intake valve is opened vacuum system, the holding temperature scope under the condition about 80～82 ℃ and vacuum tightness-0.092MP, decompression dehydration 2～3 hours.Close vacuum system then, open N
2Intake valve is at N
2Protection makes system recover normal pressure down, is cooled to 70～75 ℃.
(3) get 30g(1) in the hyperbranched polymer that synthesized, be dissolved among the 30mLDMAc, at N
2Protection drips in (2) system of reaction end down, dropwises in 0.5～1 hour, continues the control temperature at 70～75 ℃, polymerization under atmospheric pressure reaction 4～6 hours.Then close N
2Intake valve, open vacuum system, the holding temperature scope under the condition about 80～82 ℃ and vacuum tightness-0.092MP, dehydration reaction 1～3 hour, then be warming up to about 110 ℃, continue underpressure distillation and removed solvent DMAc in 1～2 hour, dripless occurs to the condenser, returns to normal pressure gradually, close vacuum system, be cooled to 60 ℃, be discharged in the plastic containers, obtain the first component.
(4) with the 135g benzoyl peroxide, and the following filler that amounts to 3500g, talcum powder, light calcium carbonate, aerosil, calcium oxide, clorafin, UV-327 UV light absorber, Rutile type Titanium Dioxide, pigment mix at a certain temperature, high-speed stirring is even, after grinding repeatedly with three-roll grinder then, pour in the plastic tank cryopreservation into.Obtain the second component.
When (5) using, first component and second component are got material by the mass ratio of 1:1.5, get the N of second constituent mass 1.5% simultaneously, and accelerine (DMA) fully mixes three material, is filled in the cement (cemented) joint.
Example 2
(1) 104 mL divinyl triamines are placed 500 mL there-necked flasks, the ice-water bath cooling is at N
2Protection down slowly drips the mixing solutions of 86 mL methyl acrylates and 200mL methyl alcohol with constant pressure funnel, reacts 4 h after dropwising at normal temperatures, obtains faint yellow transparent AB
2The type monomer, methyl alcohol is removed in underpressure distillation then, is warming up to 150 ℃ of decompression reaction 4 h again, and stopped reaction obtains the flaxen amine-terminated hyperbranced compound of thickness.In this system, add 60ml toluene as solvent, in system, slowly drip 15mL vinylformic acid then, approximately dripped 1 hour, the control temperature of reaction is at 90～120 ℃, reflux water-dividing, reacted 4～6 hours, underpressure distillation desolventizing then and excessive vinylformic acid obtain the hyperbranched polymer that end contains a small amount of amino and a large amount of-C=C.
(2) be 2000 with the 30g molecular weight, hydroxyl value is the 54-58mgKOH/g polyoxypropyleneglycol, and the 20g molecular weight is 3050, and hydroxyl value is 55-58mgKOH/g polyoxytrimethylene triol, the 15g polymerization degree is 5～7 terminal hydroxy group organosilicon, adds in the reaction vessel of dry cleansing.Under the vacuum tightness about-0.092MP, open circulating condensing water, open stirring.The control temperature is about 90 ℃, and dehydration during substantially anhydrous come out, is cooled to 50 ℃ on condenser.At N
2Protection is down opened stirring, slowly drips 10gTDI in the material that finishes to above-mentioned dehydration; strict control temperature of reaction in case the generation of implode reaction dropwises, slowly is warming up to 80～82 ℃ then in 30min about 50 ℃; keep this temperature range, polymerization under atmospheric pressure reaction 2 hours.Close N
2Intake valve is opened vacuum system, the holding temperature scope under the condition about 80～82 ℃ and vacuum tightness-0.092MP, decompression dehydration 2～3 hours.Close vacuum system then, open N
2Intake valve is at N
2Protection makes system recover normal pressure down, is cooled to 70～75 ℃.
(3) get 30g(1) in the hyperbranched polymer that synthesized, be dissolved among the 30mLDMAc, at N
2Protection drips in (2) system of reaction end down, dropwises in 0.5～1 hour, continues the control temperature at 70～75 ℃, polymerization under atmospheric pressure reaction 4～6 hours.Then close N
2Intake valve, open vacuum system, the holding temperature scope under the condition about 80～82 ℃ and vacuum tightness-0.092MP, dehydration reaction 1～3 hour, then be warming up to about 110 ℃, continue underpressure distillation and removed solvent DMAc in 1～2 hour, dripless occurs to the condenser, returns to normal pressure gradually, close vacuum system, be cooled to 60 ℃, be discharged in the plastic containers, obtain the first component.
(4) with the 135g benzoyl peroxide, and the following filler that amounts to 3500g, talcum powder, light calcium carbonate, aerosil, calcium oxide, clorafin, UV-327 UV light absorber, Rutile type Titanium Dioxide, pigment mix at a certain temperature, high-speed stirring is even, after grinding repeatedly with three-roll grinder then, pour in the plastic tank cryopreservation into.Obtain the second component.
When (5) using, first component and second component are got material by the mass ratio of 1:1, get the N of second constituent mass 1.5% simultaneously, and the N-dimethyl fully mixes three material aniline, is filled in the cement (cemented) joint.
Example 3
(1) takes by weighing 30.022g Succinic anhydried, 39.952 g diisopropanolamine (DIPA), at first diisopropanolamine (DIPA) is dissolved in 70 mLDMAc, pour into after the dissolving in the there-necked flask that has magnetic stirring apparatus, again Succinic anhydried is dissolved with 70 mLDMAc, then it is slowly dripped in the there-necked flask and stir while dripping, approximately dripped 1 hour, normal-temperature reaction 3 hours gets AB
2The type monomer.Add 60 mL toluene (toluene is the band aqua) earlier in above-mentioned system, add 1.916 g TriMethylolPropane(TMP)s as core molecule, add 0.3 g tosic acid, begin heating then, until boiling, having in the spherical condensation tube refluxes produces.After being incubated anti-7 h, in this system, slowly drip 15mL vinylformic acid, approximately dripped 1 hour, the control temperature of reaction is at 90～120 ℃, reflux water-dividing, reacted 4～6 hours, underpressure distillation desolventizing then and excessive vinylformic acid obtain the hyperbranched polymer that end contains small amount of hydroxyl groups and a large amount of-C=C.
(2) be 2000 with the 20g molecular weight, hydroxyl value is the 54-58mgKOH/g polyoxypropyleneglycol, and the 30g molecular weight is 3050, and hydroxyl value is 55-58mgKOH/g polyoxytrimethylene triol, the 15g polymerization degree is 5～7 terminal hydroxy group organosilicon, adds in the reaction vessel of dry cleansing.Under the vacuum tightness about-0.092MP, open circulating condensing water, open stirring.The control temperature is about 90 ℃, and dehydration during substantially anhydrous come out, is cooled to 50 ℃ on condenser.At N
2Protection is down opened stirring, slowly drips 15gTDI in the material that finishes to above-mentioned dehydration; strict control temperature of reaction in case the generation of implode reaction dropwises, slowly is warming up to 80～82 ℃ then in 30min about 50 ℃; keep this temperature range, polymerization under atmospheric pressure reaction 2 hours.Close N
2Intake valve is opened vacuum system, the holding temperature scope under the condition about 80～82 ℃ and vacuum tightness-0.092MP, decompression dehydration 2～3 hours.Close vacuum system then, open N
2Intake valve is at N
2Protection makes system recover normal pressure down, is cooled to 70～75 ℃.
(3) get 50g(1) in the hyperbranched polymer that synthesized, be dissolved among the 40mLDMAc, at N
2Protection drips in (2) system of reaction end down, dropwises in 0.5～1 hour, continues the control temperature at 70～75 ℃, polymerization under atmospheric pressure reaction 4～6 hours.Then close N
2Intake valve, open vacuum system, the holding temperature scope under the condition about 80～82 ℃ and vacuum tightness-0.092MP, dehydration reaction 1～3 hour, then be warming up to about 110 ℃, continue underpressure distillation and removed solvent DMAc in 1～2 hour, dripless occurs to the condenser, returns to normal pressure gradually, close vacuum system, be cooled to 60 ℃, be discharged in the plastic containers, obtain the first component.
(4) with the 135g benzoyl peroxide, and the following filler that amounts to 3500g, talcum powder, light calcium carbonate, aerosil, calcium oxide, clorafin, UV-327 UV light absorber, Rutile type Titanium Dioxide, pigment mix at a certain temperature, high-speed stirring is even, after grinding repeatedly with three-roll grinder then, pour in the plastic tank cryopreservation into.Obtain the second component.
When (5) using, first component and second component are got material by the mass ratio of 1:2, get the N of second constituent mass 2.0% simultaneously, and accelerine (DMA) fully mixes three material, is filled in the cement (cemented) joint.
Example 4
(1) takes by weighing 30.022g Succinic anhydried, 39.952 g diisopropanolamine (DIPA), at first diisopropanolamine (DIPA) is dissolved in 70 mLDMAc, pour into after the dissolving in the there-necked flask that has magnetic stirring apparatus, again Succinic anhydried is dissolved with 70 mLDMAc, then it is slowly dripped in the there-necked flask and stir while dripping, approximately dripped 1 hour, normal-temperature reaction 3 hours gets AB
2The type monomer.Add 60mL toluene (toluene is the band aqua) earlier in above-mentioned system, add the 1.916g TriMethylolPropane(TMP) as core molecule, add 0.3 g tosic acid, begin heating then, until boiling, having in the spherical condensation tube refluxes produces.After being incubated anti-7 h, in this system, slowly drip 15mL vinylformic acid, approximately dripped 1 hour, the control temperature of reaction is at 90～120 ℃, reflux water-dividing, reacted 4～6 hours, underpressure distillation desolventizing then and excessive vinylformic acid obtain the hyperbranched polymer that end contains small amount of hydroxyl groups and a large amount of-C=C.
(2) be 2000 with the 20g molecular weight, hydroxyl value is the 54-58mgKOH/g polyoxypropyleneglycol, and the 30g molecular weight is 3050, and hydroxyl value is 55-58mgKOH/g polyoxytrimethylene triol, the 5g polymerization degree is 5～7 terminal hydroxy group organosilicon, adds in the reaction vessel of dry cleansing.Under the vacuum tightness about-0.092MP, open circulating condensing water, open stirring.The control temperature is about 90 ℃, and dehydration during substantially anhydrous come out, is cooled to 50 ℃ on condenser.At N
2Protection is down opened stirring, slowly drips 10gTDI in the material that finishes to above-mentioned dehydration; strict control temperature of reaction in case the generation of implode reaction dropwises, slowly is warming up to 80～82 ℃ then in 30min about 50 ℃; keep this temperature range, polymerization under atmospheric pressure reaction 2 hours.Close N
2Intake valve is opened vacuum system, the holding temperature scope under the condition about 80～82 ℃ and vacuum tightness-0.092MP, decompression dehydration 2～3 hours.Close vacuum system then, open N
2Intake valve is at N
2Protection makes system recover normal pressure down, is cooled to 70～75 ℃.
(3) get 30g(1) in the hyperbranched polymer that synthesized, be dissolved among the 30mLDMAc, at N
2Protection drips in (2) system of reaction end down, dropwises in 0.5～1 hour, continues the control temperature at 70～75 ℃, polymerization under atmospheric pressure reaction 4～6 hours.Then close N
2Intake valve, open vacuum system, the holding temperature scope under the condition about 80～82 ℃ and vacuum tightness-0.092MP, dehydration reaction 1～3 hour, then be warming up to about 110 ℃, continue underpressure distillation and removed solvent DMAc in 1～2 hour, dripless occurs to the condenser, returns to normal pressure gradually, close vacuum system, be cooled to 60 ℃, be discharged in the plastic containers, obtain the first component.
(4) with the 135g benzoyl peroxide, and the following filler that amounts to 3500g, talcum powder, light calcium carbonate, aerosil, calcium oxide, clorafin, UV-327 UV light absorber, Rutile type Titanium Dioxide, pigment mix at a certain temperature, high-speed stirring is even, after grinding repeatedly with three-roll grinder then, pour in the plastic tank cryopreservation into.Obtain the second component.
When (5) using, first component and second component are got material by the mass ratio of 1:2, get the N of second constituent mass 1.0% simultaneously, and accelerine (DMA) fully mixes three material, is filled in the cement (cemented) joint.
Example 5
(1) takes by weighing 20.014 g Succinic anhydrieds, 26.638 g diisopropanolamine (DIPA), at first diisopropanolamine (DIPA) is dissolved in 70 mLDMAc, pour into after the dissolving in the there-necked flask that has magnetic stirring apparatus, again Succinic anhydried is dissolved with 70 mLDMAc, then it is slowly dripped in the there-necked flask and stir while dripping, approximately dripped 1 hour, normal-temperature reaction 3 hours gets AB
2The type monomer.Add 60 mL toluene (toluene is the band aqua) earlier in above-mentioned system, add 1.916 g TriMethylolPropane(TMP)s as core molecule, add 0.3 g tosic acid, begin heating then, until boiling, having in the spherical condensation tube refluxes produces.After being incubated anti-7 h, in this system, slowly drip the 8mL butenoic acid, approximately dripped 1 hour, the control temperature of reaction is at 90～120 ℃, reflux water-dividing, reacted 4～6 hours, underpressure distillation desolventizing then and excessive butenoic acid obtain the hyperbranched polymer that end contains small amount of hydroxyl groups and a large amount of-C=C.
(2) be 2000 with the 20g molecular weight, hydroxyl value is the 54-58mgKOH/g polyoxypropyleneglycol, and the 30g molecular weight is 3050, and hydroxyl value is 55-58mgKOH/g polyoxytrimethylene triol, the 15g polymerization degree is 5～7 terminal hydroxy group organosilicon, adds in the reaction vessel of dry cleansing.Under the vacuum tightness about-0.092MP, open circulating condensing water, open stirring.The control temperature is about 90 ℃, and dehydration during substantially anhydrous come out, is cooled to 50 ℃ on condenser.At N
2Protection is down opened stirring, slowly drips 10gTDI in the material that finishes to above-mentioned dehydration; strict control temperature of reaction in case the generation of implode reaction dropwises, slowly is warming up to 80～82 ℃ then in 30min about 50 ℃; keep this temperature range, polymerization under atmospheric pressure reaction 2 hours.Close N
2Intake valve is opened vacuum system, the holding temperature scope under the condition about 80～82 ℃ and vacuum tightness-0.092MP, decompression dehydration 2～3 hours.Close vacuum system then, open N
2Intake valve is at N
2Protection makes system recover normal pressure down, is cooled to 70～75 ℃.
(3) get 40g(1) in the hyperbranched polymer that synthesized, be dissolved among the 30mLDMAc, at N
2Protection drips in (2) system of reaction end down, dropwises in 0.5～1 hour, continues the control temperature at 70～75 ℃, polymerization under atmospheric pressure reaction 4～6 hours.Then close N
2Intake valve, open vacuum system, the holding temperature scope under the condition about 80～82 ℃ and vacuum tightness-0.092MP, dehydration reaction 1～3 hour, then be warming up to about 110 ℃, continue underpressure distillation and removed solvent DMAc in 1～2 hour, dripless occurs to the condenser, returns to normal pressure gradually, close vacuum system, be cooled to 60 ℃, be discharged in the plastic containers, obtain the first component.
(4) with the 135g benzoyl peroxide, and the following filler that amounts to 5400g, talcum powder, light calcium carbonate, aerosil, calcium oxide, clorafin, UV-327 UV light absorber, Rutile type Titanium Dioxide, pigment mix at a certain temperature, high-speed stirring is even, after grinding repeatedly with three-roll grinder then, pour in the plastic tank cryopreservation into.Obtain the second component.
When (5) using, first component and second component are got material by the mass ratio of 1:1.5, get the N of second constituent mass 1.5% simultaneously, and the N-Diethyl Aniline fully mixes three material, is filled in the cement (cemented) joint.
Example 6
(1) 104 mL divinyl triamines are placed 500 mL there-necked flasks, the ice-water bath cooling is at N
2Protection down slowly drips the mixing solutions of 86 mL methyl acrylates and 200mL methyl alcohol with constant pressure funnel, reacts 4 h after dropwising at normal temperatures, obtains faint yellow transparent AB
2The type monomer, methyl alcohol is removed in underpressure distillation then, is warming up to 150 ℃ of decompression reaction 4 h again, and stopped reaction obtains the flaxen amine-terminated hyperbranced compound of thickness.In this system, add 60mL toluene as solvent, in system, slowly drip 15mL2-methyl-4-pentenoic acid then, approximately dripped 1 hour, the control temperature of reaction is at 90～120 ℃, reflux water-dividing, reacted 4～6 hours, underpressure distillation desolventizing then and excessive 2-methyl-4-pentenoic acid obtain the hyperbranched polymer that end contains a small amount of amino and a large amount of-C=C.
(2) be 2000 with the 10g molecular weight, hydroxyl value is the 54-58mgKOH/g polyoxypropyleneglycol, and the 40g molecular weight is 3050, and hydroxyl value is 55-58mgKOH/g polyoxytrimethylene triol, the 15g polymerization degree is 5～7 terminal hydroxy group organosilicon, adds in the reaction vessel of dry cleansing.Under the vacuum tightness about-0.092MP, open circulating condensing water, open stirring.The control temperature is about 90 ℃, and dehydration during substantially anhydrous come out, is cooled to 50 ℃ on condenser.At N
2Protection is down opened stirring, slowly drips 10gTDI in the material that finishes to above-mentioned dehydration; strict control temperature of reaction in case the generation of implode reaction dropwises, slowly is warming up to 80～82 ℃ then in 30min about 50 ℃; keep this temperature range, polymerization under atmospheric pressure reaction 2 hours.Close N
2Intake valve is opened vacuum system, the holding temperature scope under the condition about 80～82 ℃ and vacuum tightness-0.092MP, decompression dehydration 2～3 hours.Close vacuum system then, open N
2Intake valve is at N
2Protection makes system recover normal pressure down, is cooled to 70～75 ℃.
(3) get 30g(1) in the hyperbranched polymer that synthesized, be dissolved among the 30mLDMAc, at N
2Protection drips in (2) system of reaction end down, dropwises in 0.5～1 hour, continues the control temperature at 70～75 ℃, polymerization under atmospheric pressure reaction 4～6 hours.Then close N
2Intake valve, open vacuum system, the holding temperature scope under the condition about 80～82 ℃ and vacuum tightness-0.092MP, dehydration reaction 1～3 hour, then be warming up to about 110 ℃, continue underpressure distillation and removed solvent DMAc in 1～2 hour, dripless occurs to the condenser, returns to normal pressure gradually, close vacuum system, be cooled to 60 ℃, be discharged in the plastic containers, obtain the first component.
(4) with the 135g dilauroyl peroxide, and the following filler that amounts to 2700g, talcum powder, light calcium carbonate, aerosil, calcium oxide, clorafin, UV-327 UV light absorber, Rutile type Titanium Dioxide, pigment mix at a certain temperature, high-speed stirring is even, after grinding repeatedly with three-roll grinder then, pour in the plastic tank cryopreservation into.Obtain the second component.
When (5) using, first component and second component are got material by the mass ratio of 1:1.5, get the N of second constituent mass 1.5% simultaneously, and accelerine (DMA) fully mixes three material, is filled in the cement (cemented) joint.
Polyurethane filling material to above-mentioned example has carried out performance test, data such as following table:
| ? | Maximum elongation rate % | Tensile strength MPa | Cohesive strength MPa | Penetration degree mm | Hot pressing-cold drawn circulation | Aged properties % |
| 1 | 930 | 1.46 | 0.40 | 2.2 | Can carry out at 100% time | Every property retention is about 80% |
| 2 | 980 | 1.34 | 0.35 | 2.6 | Can carry out at 100% time | Every property retention is about 75% |
| 3 | 850 | 1.53 | 0.44 | 1.7 | Can carry out at 100% time | Every property retention is about 70% |
| 4 | 900 | 1.38 | 0.36 | 2.0 | Can carry out at 100% time | Every property retention is about 80% |
| 5 | 910 | 1.41 | 0.32 | 2.5 | Can carry out at 100% time | Every property retention is about 75% |
| 6 | 880 | 1.63 | 0.41 | 1.9 | Can carry out at 100% time | Every property retention is about 70% |
Claims (8)
1. a cement pavement gap-filling glue that replaces the NCO crosslinking curing is characterized in that being made up of first component, second component and amine type accelerator,
Described first component obtains base polyurethane prepolymer for use as by the copolymerization under the effect of catalyzer Benzoyl chloride of polyether glycol, terminal hydroxy group organosilicon and isocyanic ester, obtain with the hyperbranched polymer polymerization of end with the olefin(e) acid partial esterification then, the end of described hyperbranched polymer is hydroxyl;
Described second component is mixed by peroxide catalyst and filler,
Wherein first component and second constituent mass are than being 1:1～2, and amine type accelerator is 1.0%～2.0% of second constituent mass;
Terminal hyperbranched polymer with the olefin(e) acid partial esterification, C-terminal is 1:5～11 with the number ratio of ester group end,
Polyether glycol, isocyanic ester, terminal hydroxy group organosilicon, end are 10:2～3:1～3:6～10 with the weight ratio of the hyperbranched polymer of olefin(e) acid partial esterification in the described first component.
2. cement pavement gap-filling glue according to claim 1, it is characterized in that the weight ratio of catalyzer and filler is 1:20～40 in the second component, filler is more than one in talcum powder, light calcium carbonate, aerosil, calcium oxide, clorafin, UV light absorber, the pigment.
3. cement pavement gap-filling glue according to claim 1 is characterized in that peroxide catalyst is dibenzoyl peroxide or dilauroyl peroxide.
4. cement pavement gap-filling glue according to claim 1, the hydroxyl value that it is characterized in that polyether glycol is 30～70mgKOH/g, and described terminal hydroxy group polymerizable organosilicon degree is 5～10, and described isocyanic ester is polyisocyanates.
5. cement pavement gap-filling glue according to claim 1 is characterized in that superbrnaching end-hydroxy polymkeric substance hydroxyl value is 19～46mgKOH/g.
6. cement pavement gap-filling glue according to claim 1 is characterized in that amine type accelerator is N, accelerine or N, N-Diethyl Aniline.
7. cement pavement gap-filling glue according to claim 1 is characterized in that hyperbranched polymer prepares by following method:
30.022g Succinic anhydried, the reaction of 39.952 g diisopropanolamine (DIPA) are obtained AB
2The type monomer adds 1.916 g TriMethylolPropane(TMP)s as core molecule, adds the reaction of 0.3 g tosic acid and obtains the superbrnaching end-hydroxy polymkeric substance.
8. cement pavement gap-filling glue according to claim 1 is characterized in that the hyperbranched polymer polymerization process of base polyurethane prepolymer for use as and terminal portions esterification is as follows:
Get terminal hyperbranched polymer with the olefin(e) acid partial esterification, dissolving is at N
2Protection drips in base polyurethane prepolymer for use as down, drips off at 0.5～1 hour, and 70～75 ℃ of polymerization under atmospheric pressure reactions 4～6 hours, the desolventizing that dewaters then obtained the first component.
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| CN102964810A (en) * | 2012-11-15 | 2013-03-13 | 北京橡胶工业研究设计院 | Polyurethane rubber composition |
| CN103408924B (en) * | 2013-07-10 | 2015-08-19 | 万铜岭 | Joint closure material |
| CN103360564B (en) * | 2013-07-17 | 2015-12-02 | 济南大学 | A kind of hyperbranched non-ionic water polyurethane and the application in glass fiber infiltration agent thereof |
| CN103803840B (en) * | 2014-01-27 | 2016-05-04 | 济南大学 | The application of dissaving polymer in economization agent for concrete |
| CN105733490B (en) * | 2016-03-25 | 2018-05-04 | 济南大学 | A kind of cement concrete pavement gap-filling glue of moisturecuring self-crosslinking |
| CN105754537B (en) * | 2016-03-28 | 2019-05-07 | 山西四方恒泰防水材料有限公司 | A kind of preparation method of joint filling sealing material |
| CN107200849B (en) * | 2017-05-17 | 2020-06-09 | 江苏超力建材科技有限公司 | Water-based interface agent for cement highway joint and preparation method and application thereof |
| CN109053067B (en) * | 2018-08-15 | 2020-06-02 | 中国葛洲坝集团第一工程有限公司 | Grouting slurry and application thereof in cement-stabilized gravel layer parting construction process |
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| CN101709039A (en) * | 2009-07-07 | 2010-05-19 | 济南大学 | Hyperbranched curing agent for two-component polyurethane waterproof coating and preparation method thereof |
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| WO2008075806A1 (en) * | 2006-12-19 | 2008-06-26 | Hak Soo Han | Photo-curable coating composition comprising hyperbranched structure prepolymer, method for preparing the same and product prepared by the same |
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| CN101709039A (en) * | 2009-07-07 | 2010-05-19 | 济南大学 | Hyperbranched curing agent for two-component polyurethane waterproof coating and preparation method thereof |
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