CN102796243A - Polyurethane modified epoxy resin adhesive, and preparation method and application thereof - Google Patents
Polyurethane modified epoxy resin adhesive, and preparation method and application thereof Download PDFInfo
- Publication number
- CN102796243A CN102796243A CN201110135746XA CN201110135746A CN102796243A CN 102796243 A CN102796243 A CN 102796243A CN 201110135746X A CN201110135746X A CN 201110135746XA CN 201110135746 A CN201110135746 A CN 201110135746A CN 102796243 A CN102796243 A CN 102796243A
- Authority
- CN
- China
- Prior art keywords
- component
- epoxy resin
- weight
- epoxy
- polyurethane prepolymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a polyurethane modified epoxy resin adhesive for a colored antiskid road surface. The polyurethane modified epoxy resin adhesive comprises an epoxy resin mixture component A and a polyurethane modified amine hardener component B, wherein the component A comprises bisphenol A-type epoxy resin and polypropylene glycol diglycidyl ether; the component B consists of organic polyamine, bisphenol A-type epoxy resin, polyoxypropylene glycol, diphenylmethane diisocyanate, an ultraviolet absorbent, a plasticizer and a solvent; the component A and the component B are separately stored; and during use, the component A and the component B are mixed for use according to a weight ratio of 100:100. The polyurethane modified epoxy resin adhesive can be used for paving the colored antiskid road surface.
Description
Technical field
The present invention relates to a kind of polyurethane modified epoxy resin tackiness agent, its preparation method and the application in anti-skid surface thereof.
Technical background
Current; The road traffic in China city problem of blocking up is more and more serious; But China and many in the world national practice results and empirical evidence; Road traffic accident can prevent and control, and wherein adopting effective road surface antiskid system, especially colored road surface antiskid system is a preferable measure.
The colored road surface antiskid system is a kind of resin base road surface antiskid system, comprises that the resin-based adhesive of special formulation and the aggregate of various different sizes are equipped with the pigment of being convenient to discern, and is coated on pitch or cement pavement with accurate quantity and forms.At motorway culvert, permeable road and, car lane, road cross, bend slope road and sign isolation strip etc. need the occasion of the anti-slip pervious decorations of safety; Color anti-skid road surface goes on the road surface of regulation through the difference prompting driver of road color; Thereby avoided the mixed row of different vehicle, and played fine skidproof effect through the surface layer that high frictional force is provided.The officer sails above-mentioned highway section into and can underspeed in advance, and in case of emergency, shortens braking distance, and generation avoids traffic accident.
Lay colored road surface and adopt color asphalt method and colo(u)r coating method usually.The color asphalt method is that decolouring pitch is processed in the pitch decarburization, adds then to pave with the aggregate mix after pigment is processed color asphalt again.Its advantage is to carry out mechanized construction according to the constructional method of plain asphalt, but have that non-skid property is bad, the bright-coloured inadequately abundant and shortcoming such as persistence is poor and laying depth is thicker of color.The colo(u)r coating method normally adopts colored acrylic to be coated with as tackiness agent and is layered on the road surface, sprinkles anti-skidding sand or anti-skidding aggregate then in the above, carries out cover at surfaces coated last layer colored acrylic more at last.The advantage of this method is that set time is fast and construction is simple, and is bigger to the alternative of color; Shortcoming is because easy deliquescing distortion under the limited and high temperature of the cohesive strength of acrylics own causes it to be applicable to that some are to the less demanding underloading traffic road surface of non-skid property.
Summary of the invention
For overcoming the above-mentioned defective of prior art, one of the object of the invention is to provide a kind of polyurethane modified epoxy resin tackiness agent that can be used for anti-skid surface of environmental protection.
Another object of the present invention is to provide a kind of preparation method of above-mentioned polyurethane modified epoxy resin tackiness agent.
A purpose more of the present invention is to provide the application of above-mentioned tackiness agent in the antiskid road road surface, the especially colored road surface that carry communications and transportation.
For realizing above-mentioned purpose, the present invention adopts following technical scheme:
A kind of polyurethane modified epoxy resin tackiness agent, it comprises component A and B component, wherein
Component A is an epoxy resin composition, and it comprises:
(i) 100 weight part oxirane values are the bisphenol A type epoxy resin of 0.41-0.58mol/100g;
(ii) 1-20 parts by weight average molecular weight is the polypropylene glycol diglycidyl ether of 100-1000, is used to regulate the viscosity of component A;
B component is polyurethane-modified amine hardener, and it comprises:
(i) organic polyamine of 100 weight parts,
This organic polyamine be selected from down the group at least a: fatty amine, cycloaliphatic amines, aromatic amine, modified amine epoxy curing agent and their mixture;
The (ii) epoxy polyurethane prepolymer of 40-70 weight part,
This epoxy polyurethane prepolymer is mixed by the base polyurethane prepolymer for use as of 100 weight parts and the bisphenol A type epoxy resin of 40-70 weight part (oxirane value is 0.41-0.58mol/100g) add the 80-120 weight part again after polyreaction softening agent,
Wherein said base polyurethane prepolymer for use as by one or more diphenylmethanediisocyanates (MDI) and one or more number-average molecular weights be the polyvalent alcohol of 1000-10000 by 100: the 200-2000 part by weight is through being polymerized, and its isocyano (NCO) content is 0.5-6wt%;
The (iii) UV light absorber of 0.5-5 weight part;
The (iv) solvent of the solubilized epoxy polyurethane prepolymer of 15-30 weight part is used to regulate the viscosity of B component;
Component A and B component are deposited with being separated, during use by component A: B component is that 100: 100 weight ratio is used.
A kind of method for preparing above-mentioned polyurethane modified epoxy resin tackiness agent comprises the steps:
(1) preparation of component A:
The bisphenol A type epoxy resin (oxirane value is 0.41-0.58mol/100g) of 100 weight parts and the polypropylene glycol diglycidyl ether (number-average molecular weight 100-1000) of 1-20 weight part are stirred under 60-80 ℃ temperature; Get epoxy resin composition; Epoxy equivalent (weight) is 160-260; Pack after being cooled to room temperature, sealing is deposited;
(2) preparation of B component
1. prepare base polyurethane prepolymer for use as:
The polyvalent alcohol that took off water that with at least a number-average molecular weight of at least a diphenylmethanediisocyanate (MDI) of 100 weight parts and 200-2000 weight part is 1000-10000 is 60-90 ℃ of reaction 1-4 hour down; Generate isocyanate-terminated performed polymer, isocyano (NCO) content is 0.5-6wt%;
2. prepare the epoxy polyurethane prepolymer
The above-mentioned base polyurethane prepolymer for use as of 100 weight parts and the bisphenol A type epoxy resin of 40-70 weight part (oxirane value is 0.41-0.58mol/100g) were reacted 1-4 hour under 60-90 ℃ of temperature; When NCO content drops to 0%; The softening agent that adds the 80-120 weight part; Form the epoxy polyurethane prepolymer, epoxy equivalent (weight) is 800-1600;
3. prepare polyurethane-modified amine hardener
The organic polyamine of 100 weight parts is warming up to 80-100 ℃, slowly adds the above-mentioned epoxy polyurethane prepolymer of 40-70 weight part, after reacting 1-2 hour under this temperature; The UV light absorber that adds the 0.5-5 weight part again; Stirred 0.25-0.5 hour, guarantee that UV light absorber dissolves fully after, temperature of reaction is dropped to 60-80 ℃; Add the solvent adjustment viscosity of 15-30 weight part solubilized epoxy polyurethane prepolymer at last, the amine value is 180-280mgKOH/g;
Tackiness agent of the present invention is a kind of polyurethane modified epoxy resin multipolymer of uniqueness; Can good cohesive force be arranged with concrete, pitch, abrasion resistant particles and stone material etc.; Weather-resistant; Good toughness makes it have anti-roadbed rimose performance, is applicable to easily advantages such as construction technology and curing time be short.
Embodiment
Below in conjunction with specific embodiment, the present invention is described further.Should be understood that following examples only to be used to the present invention is described and be not used in the scope of the present invention that limits.
Among this paper, " MDI " is the abbreviation of " diphenylmethanediisocyanate ", and such as 2,4-MDI is meant 2, the 4-diphenylmethanediisocyanate, and 4,4 '-MDI is meant 4,4 '-diphenylmethanediisocyanate; " NCO " is the abbreviation of " isocyano ".
" part " described in this paper except that specifying, all refers to " weight part "; Described percentage composition except that specifying, all refers to weight percentage;
The composition of component A and preparation
Component A of the present invention is a composition epoxy resin, and its preparation raw material comprises: oxirane value is that bisphenol A epoxide resin and the number-average molecular weight of 0.41-0.58mol/100g is the polypropylene glycol diglycidyl ether of 100-1000.
Wherein, the oxirane value of bisphenol A type epoxy resin is 0.41-0.58mol/100g.The following 0.41mol/100g that is limited to of this oxirane value, more preferably 0.42,0.43,0.44,0.45,0.46,0.47,0.48,0.49 or 0.50mol/100g; Be limited to 0.58mol/100g on this oxirane value, more preferably 0.56,0.55,0.54,0.53,0.52,0.52 or 0.51mol/100g.
The method that this epoxy resin can be known by one of skill in the art is synthetic.For example, adopt two-step process, with dihydroxyphenyl propane and epoxy chloropropane catalyzer such as the quaternary ammonium salt effect under, the first step is through addition reaction generation diphenylol propane chloropharin ether midbody, second goes on foot and in the presence of NaOH, reacts generation epoxy resin.
In a kind of embodiment, the bisphenol A epoxide resin that is used to form component A of the present invention is to be selected from down at least a in the group: E-42 epoxy resin, be called for short E-42, and oxirane value is 0.38-0.45mol/100g, epoxy equivalent (weight) is 222-263; E-44 epoxy resin is called for short E-44, and oxirane value is 0.41-0.47mol/100g, and epoxy equivalent (weight) is 212-244; E-51 epoxy resin is called for short E-51, and oxirane value is 0.48-0.54mol/100g, and epoxy equivalent (weight) is 185-208; E-55 epoxy resin is called for short E-55, and oxirane value is 0.55-0.56mol/100g, and epoxy equivalent (weight) is 178-182.
The polypropylene glycol diglycidyl ether that uses among the present invention, as the viscosity that thinner is used to regulate component A, number-average molecular weight is 100-1000.The following of number-average molecular weight is limited to 100, and more preferably 120,150,180,200,220,250,280,300,320,350,380,400,420,450,480,500; Be limited to 1000 on the number-average molecular weight, more preferably 980,950,920,900,880,850,820,800,780,750,720,700,680,650,620,600.
In a kind of embodiment, be used to form polypropylene glycol diglycidyl ether of the present invention and be and be selected from down at least a in the group: glycidyl ether, number-average molecular weight are 130; Propylene glycol diglycidylether, number-average molecular weight are 246; Polypropylene glycol diglycidyl ether 6360, number-average molecular weight are 360; Polypropylene glycol diglycidyl ether PEGGE-400, number-average molecular weight is 600.
In the bisphenol A epoxide resin of 100 weight parts, the content of this thinner is the 1-20 weight part.If the content of polypropylene glycol diglycidyl ether is less than 1 weight part, then component A viscosity is excessive, is difficult for mixing with aggregate, causes the waste in the construction easily simultaneously, and influences the product use; If the content of polypropylene glycol diglycidyl ether is higher than 20 weight parts, then can prolong the products solidifying time etc.The content of preferred polypropylene glycol diglycidyl ether is the 1-15 weight part, preferred 1.2-10 weight part, more preferably 1.5-5 weight part, more preferably 1.8-4 weight part, more preferably 2-3 weight part.
The preparation of component A is that bisphenol A type epoxy resin and polypropylene glycol diglycidyl ether are mixed under 60-80 ℃ temperature and get, and preferred mixing temperature is 65-78 ℃, more preferably 68-75 ℃.
The epoxy equivalent (weight) of component A is 160-260, preferred 170-250, more preferably 180-240, more preferably 190-230, more preferably 200-220.
The composition of B component and preparation
The preparation raw material of polyurethane-modified amine hardener comprises among the present invention: organic polyamine; Bisphenol A type epoxy resin, diphenylmethanediisocyanate (MDI), number-average molecular weight are polyvalent alcohol, softening agent, the UV light absorber of 1000-10000, the solvent of solubilized epoxy polyurethane prepolymer.
Being used for organic polyamine of the present invention is meant and contains more than two-NH
2Group ,-fatty amine of NHR group, cycloaliphatic amines, aromatic amine, amine epoxy curing agent modified, aliphatic amine, cycloaliphatic amines, amine epoxy curing agent modified, more preferably commercial amine epoxy curing agent modified.
Such as organic polyamine be selected from down the group at least a:
Quadrol, hexanediamine, 1; 3-tn, new pentamethylene diamine, diethylenetriamine, triethylene tetramine, TEPA, five ethene hexamines, two propylene triamines, DIMAPA, diethyl amino propylamine, the basic triamine of trimethylhexamethylenediamine, two, two amine adducts (trade(brand)name: L2505; Amine value 160-210), trimethylammonium diamines, polyethylene polyamine (trade(brand)name: E-100; The amine value is 1257mgKOH/g), commercial modification cycloaliphatic amines epoxy solidifying agent (trade(brand)name: R-2253 amine value: 320mgKOH/g), commercial modified aliphatic amine epoxy curing agent (trade(brand)name: R-2011; The amine value is 392mgKOH/g), polypropylene glycol diamine (trade(brand)name: DA-400; Data molecular weight 400), polypropylene glycol diamine (trade(brand)name: DA-1000; Number-average molecular weight 1000), polypropylene glycol diamine (trade(brand)name: DA-2000; Data molecular weight 2000), N-methylol diethyl triamine, N-methylol quadrol, N-N-aminoethyl ethanolamine, N; N '-dihydroxy ethyl quadrol, N-hydroxyethyl diethylenetriamine, N; N '-dihydroxy ethyl diethylenetriamine, N-hydroxyethyl diamines, a cyanoethyl quadrol, a cyanoethyl diamines, dicyanoethyl quadrol, a cyanoethyl diethylenetriamine, two cyanoethyl diethylenetriamine, diaminomethyl cyclohexane, the Meng alkane diamines, aminoethyl croak piperazine, hexahydropyridine, isophorone diamine, diamino-cyclohexane, diaminomethyl cyclohexyl methane, diamino-cyclohexyl methane, mphenylenediamine, m-xylene diamine, diaminodiphenyl-methane, diamino diphenyl sulfone, m-aminophenyl methylamine, p-diaminodiphenyl, SKF 199 base ether, mphenylenediamine and diaminodiphenyl-methane mixture (weight ratio 100: 30-70), (weight ratio is 30-70: 30-75: 15-50), ortho-toluene diamine, toluylenediamine and diaminodiphenyl-methane mixture (weight ratio 100: 50-60: 200-260), diaminodiphenyl-methane and isophorone diamine mixture (weight ratio 100: 150-250), P-F-diethylenetriamine condenses (trade(brand)name: T-31, amine value 360-450) for mphenylenediamine and diaminodiphenyl-methane and tolylene diamine mixture.
In a kind of embodiment; The diphenylmethanediisocyanate (MDI) that is used to form base polyurethane prepolymer for use as be selected from down the group at least a: 4; 4 '-diphenylmethanediisocyanate (trade(brand)name: MDI-100,
1810), 2,4-diphenylmethanediisocyanate (trade(brand)name:
3051,
3056), carbodiimide diphenylmethanediisocyanate (trade(brand)name:
2020) and composition thereof.
The polyvalent alcohol that is used to form base polyurethane prepolymer for use as is polyether polyol or polyester polyol, and number-average molecular weight is 1000-10000.The following of the number-average molecular weight of this polyvalent alcohol is limited to 1000, is preferably 1100,1200,1300,1400,1500,1600,1700,1800,1900,2000,2100,2200,2300,2400,2500,2600,2700,2800,2900,3000; Be limited to 10000 on the number-average molecular weight, be preferably 9000,8500,8000,7500,7000,6500,6000,5500,5000,4500.
In a kind of embodiment, polyvalent alcohol be selected from down the group at least a: polyoxytrimethylene ether glycol (number-average molecular weight 1000, trade(brand)name PPG-210; Number-average molecular weight 2000, trade(brand)name PPG-220; Number-average molecular weight 4000, trade(brand)name PPG-2028), polycaprolactone glycol (number-average molecular weight 1000, trade(brand)name PCL-210; Number-average molecular weight 2000, trade(brand)name PCL-220), poly adipate succinic acid ester (number-average molecular weight 1000, trade(brand)name P-144; Number-average molecular weight 2000, trade(brand)name P-244), PTMG (data molecular weight 1000, trade(brand)name PTMG-1000; Data molecular weight 2000, trade(brand)name PTMG-2000).
The preparation of base polyurethane prepolymer for use as can be adopted the confessed polymerization method in this area, such as " plastics industry handbook (urethane): chapter 10 polyurethane elastomer " (Li Junxian chief editor, Chemical Industry Press, the 1st edition, 1999, the related preparation technology of P406) introducing.
Specifically, its preparation mainly comprises: earlier polyvalent alcohol is carried out processed, avoid causing because of the existence of water the side reaction generation of polyureas, and then cause the performed polymer quality to descend; Elder generation such as being heated to 60 ℃, avoids the MDI preheating to cause performed polymer MWD ununiformity and quality unstable greatly because of temperature variation before carrying out polyreaction.
In the base polyurethane prepolymer for use as preparation, the weight ratio of diphenylmethanediisocyanate and polyvalent alcohol is 100: 200-2000; More preferably 100: 350-850; More preferably 100: 400-800.If the umber of polyvalent alcohol is too high, then can causes NCO content to reduce, even cause gel; If the umber of polyvalent alcohol is low excessively, side reaction then takes place easily.
The base polyurethane prepolymer for use as that diphenylmethanediisocyanate and polyol reaction generated is isocyanate-terminated performed polymer, and isocyano (NCO) content is 0.5-6wt%.Preferred NCO content is 0.8-6wt%; More preferably 1-5wt%; More preferably 1.2-4.8wt%; More preferably 1.3-4.5wt%; More preferably more preferably 1.8-3.5wt% of 1.5-4wt%.If NCO content is higher than 6wt%, then reduced soft section content of final polymkeric substance, do not reach toughness reinforcing purpose; If NCO content is lower than 0.5wt%, then the reactivity with bisphenol A epoxide resin reduces, and the modification degree of epoxy resin is reduced, and package stability descends, and causes easily to be separated.
The polyreaction of diphenylmethanediisocyanate and polyvalent alcohol is controlled at 50-100 ℃, and preferred 60-90 ℃, more preferably 60-85 ℃.If be lower than 60 ℃, react not thorough, influence molecular weight and distribution thereof; If be higher than 85 ℃, cause the side reaction allophanate to produce easily.Reaction times is 1-4 hour, if it is not thorough to be less than reaction in 1 hour, influences molecular weight and distribution thereof; If surpass 4 hours, the side reaction that then possibly cause generating uretdione takes place.
The end group of the molecular chain of epoxy polyurethane prepolymer of the present invention is an epoxy group(ing), is formed through polyreaction by base polyurethane prepolymer for use as and bisphenol A type epoxy resin, after reaction finishes, adds softening agent to reduce the viscosity of this prepolymer.
In the preparation of this prepolymer; Used bisphenol A epoxide resin can be identical with the used bisphenol A epoxide resin of component A, such as being to be selected from down at least a in the group: and E-42 epoxy resin, be called for short E-42; Oxirane value is 0.38-0.45mol/100g, and epoxy equivalent (weight) is 222-263; E-44 epoxy resin is called for short E-44, and oxirane value is 0.41-0.47mol/100g, and epoxy equivalent (weight) is 212-244; E-51 epoxy resin is called for short E-51, and oxirane value is 0.48-0.54mol/100g, and epoxy equivalent (weight) is 185-208; E-55 epoxy resin is called for short E-55, and oxirane value is 0.55-0.56mol/100g, and epoxy equivalent (weight) is 178-182.
In the preparation of this prepolymer, the weight ratio of base polyurethane prepolymer for use as and bisphenol A type epoxy resin is 100: 40-70; Preferred 100: 45-65.More preferably 100: 50-60, if the umber of epoxy resin is low excessively, then the system degree of crosslinking is excessive, is prone to take place gel; If the umber of epoxy resin is too high, then the relative content of urethane has just reduced, and finally influences product in the toughness of solidifying the after fixing thing.
The polyreaction of base polyurethane prepolymer for use as and bisphenol A type epoxy resin is controlled at 60-90 ℃, and preferred 60-85 ℃, more preferably 70-85 ℃.If be lower than 60 ℃, react not thorough, the reaction times can prolong, if be higher than 90 ℃, causes side reaction to cause jello to form easily.Reaction end as criterion, in the time of 80 ℃, was accomplished entire reaction course about 4 hours with NCO=0%.
In the preparation of this prepolymer, selected softening agent is one or more in phthalic acid two (just) butyl ester, phthalic acid two (just) monooctyl ester, epoxy soybean oil, carbonic acid allyl ester, the adipic acid di-isooctyl.
The weight ratio of base polyurethane prepolymer for use as and softening agent is 100: 80-120; Preferred 100: 80-110, more preferably 100: 90-100; If the umber of softening agent is too high, then the tackiness agent bonding strength descends, and causes easy deliquescing distortion under the high temperature of road surface, and non-skid finish can come off from the road surface; If the umber of softening agent is low excessively, then viscosity increase be unfavorable for pavement construction and with the combining of aggregate.
The epoxy polyurethane prepolymer epoxy equivalent (weight) of preparation is 800-1600, preferred 900-1500, more preferably 1000-1400, more preferably 1100-1300.In the preparation of B component, the weight ratio of organic polyamine and epoxy polyurethane prepolymer is 100: 40-70; Preferred 100: 50-70 more preferably 100: 50-65.If the umber of epoxy polyurethane prepolymer is too high, then the system instability causes B component gel in producing and storing; If the umber of epoxy polyurethane prepolymer is low excessively, then do not have toughness reinforcing effect.
The UV light absorber that is used for preparing B component can be a kind of of UV-328 and UV-320 or their mixture.
In the preparation of B component, the weight ratio of organic polyamine and UV light absorber is 100: 0.5-5; More preferably 100: 0.8-4; Further preferred 100: 1-3; More preferably 100: 2-3.
Solvent in the B component is the solvent of solubilized epoxy polyurethane prepolymer; Comprise ketone, ester class, ether alcohol class, amides and aromatic hydrocarbons etc.; Preferably be selected from down one or more the mixture in the group: such as acetone, butanone, pimelinketone,, N-N-methyl-2-2-pyrrolidone N-, ETHYLE ACETATE, butylacetate, Isoamyl Acetate FCC, THF, dioxane, ethylene glycol monomethyl ether, propylene glycol monobutyl ether, N; Dinethylformamide, DMAC N,N, toluene, YLENE.Consider from environmental protection, in conjunction with the surface properties of cement pavement, bituminous pavement, more preferably N, dinethylformamide or N-N-methyl-2-2-pyrrolidone N-or both mixtures.
In the preparation of B component, the weight ratio of organic polyamine and solvent is 100: 15-30.If the content of solvent is less than 15 weight parts, then B component viscosity is excessive and can not make aggregate obtain the fully wetting bonding strength that causes well to descend, and influence the product use; If the content of solvent is higher than 30 weight parts, then can cause B component viscosity too small, cause prolong set time.
B component prepares through following steps: after making organic polyamine be warming up to 80-100 ℃; Slowly add the epoxy polyurethane prepolymer; Under this temperature, react, add UV light absorber then, be stirred to UV light absorber and dissolve fully; Again temperature of reaction is dropped to 60-80 ℃, add solvent adjustment viscosity at last.Resulting epoxy polyurethane prepolymer amine value is 180-280mgKOH/g, preferred 190-270mgKOH/g, more preferably 200-260mgKOH/g, more preferably 210-250mgKOH/g.
Use of the present invention
Tackiness agent of the present invention uses with aggregate usually, is coated on concrete road surface, bituminous pavement, ground mass road surface, porcelain base road surface, the brick base road surface, and forms good cohesive force with these road surfaces.
Tackiness agent of the present invention can mix various colorants as required and use together, so that form needed colored road surface.
The aggregate that is used for the making color anti-skid road surface answers entire body of the same colour, and is dry dustless, squarish, and median size is no more than 4mm, is advisable with 1-3mm, and Mohs' hardness is more than 6.Can select for use through high-temperature calcination and painted colored ceramic particle.By component A: B component is after 100: 100 weight ratio mix evenly forms the fluid of homogeneous it to be paved in the road surface, sheds colored aggregate through artificial or machine, guarantees that the latter covers on it fully, promptly forms versicolor color anti-skid road surface after the curing.
Antislip colour Lu Eryong polyurethane modified epoxy resin tackiness agent is a kind of two-component-type colored road surface material, and it is liquid.During construction, need not main equipment, only need, be coated with the mode of roller coating and be laid on the road surface, and add the antislip colour aggregate behind component A and the B component proportional mixing, the process chemical crosslink reaction, fast setting becomes tough and tensile glued membrane, the formation colored road surface.
Tackiness agent of the present invention is preferably in the self-vulcanizing moulding.
Adopt technical scheme of the present invention, compared with prior art, adhesive compound of the present invention has conspicuous following advantage:
(1) B component is the modifier of urethane, and the water quality and the atmospheric pollution that have brought when having avoided pungent migration and volatilization have more environment friendly.
(2) said composition viscosity is low, can under relatively low temperature, process, and can room temperature fast-curing, glue-applying technique is easy, has significantly reduced energy consumption, has improved production efficiency.
(3) adhesive compound had both kept the higher characteristics of epoxy bond intensity, had increased the toughness of cured article through introducing urethane again, made it have higher mechanical property and good high and low temperature resistance.
Below embodiment will be used for illustrating the present invention, but be not to be used for limiting claim scope of the present invention, except as otherwise noted, the umber of addressing among the following embodiment all refers to weight part.
The color anti-skid road surface that following each embodiment is obtained sticks with glue the testing evaluation that following technical indicator is carried out in agent.
Test index comprises:
Epoxy equivalent (weight) is pressed GB/T 4612-2008 test;
Isocyano-content (NCO content) is pressed GB 12009.4-89 test;
The method test that the amine value is described by " coating technology and digest " 2004 the 25th the 1st phases of volume 40-41 page or leaf;
Ultimate tensile strength, elongation at break, hardness and ultimate compression strength are pressed ASTM D638 test;
Gel time is measured with reference to the manual method test in the GB/T 7193.6-1987 testing standard; Evenly be poured in the metal die of 25 ℃ of constant temperature, volume 200mm * 200mm * 10mm the test stringy time after mixing with 100g component A with the 100g B component;
Setting time is tested with reference to the fingers-touch method in the GB 1728-1979 testing standard;
Shore hardness A presses the TP of Shao Shi A regulation in GB/T 2411 testing standards;
Sliding resistance, water tolerance, alkali resistance and low-temperature cracking-resistance are pressed the JT/T712-2008 test.
Embodiment 1
1. the preparation of component A
The polypropylene glycol diglycidyl ether 6360 of 100 parts E-51 epoxy resin and 10 parts is stirred under 60-80 ℃ temperature, epoxy resin composition, the test epoxy equivalent (weight) is 207.Pack after being cooled to room temperature, sealing is deposited.
2. B component is synthetic
(1) dehydration of polyvalent alcohol: polyoxytrimethylene ether glycol PPG-2028 (the data molecular weight 4000) input with capacity has in the vacuum reaction still of stirring earlier; Be heated to 120 ℃ under stirring; Be evacuated to then-0.09mPa, dewatered 120 minutes, it is for use to be cooled to room temperature then.
(2) preparation of base polyurethane prepolymer for use as: with 100 parts 2; 4-diphenylmethanediisocyanate
3056 is put in another reaction kettle; Under nitrogen protection; Stirring is warming up to 60 ℃; Slowly add (1) set by step then and took off 800 parts of PPG-2028 polyoxytrimethylene ether glycol of water, feed rate is the best with temperature of reaction kettle at 80～85 ℃, wait to add polyoxytrimethylene ether glycol after; Continue reaction 4 hours, surveying NCO content is 1.86wt%.
(3) preparation of epoxy polyurethane prepolymer: with the E-51 epoxy resin of the base polyurethane prepolymer for use as of 100 parts above-mentioned steps (2) and 57 parts stirring reaction 4 hours under 80-85 ℃ of temperature; Surveying NCO content is 0%; Show that reaction accomplishes; The carbonic acid allyl ester that adds 93 parts again forms epoxy polyurethane resin prepolymer, and epoxy equivalent (weight) is 910.
(4) preparation of polyurethane-modified amine hardener: (trade(brand)name: R-2011, the amine value is 392mg KOH/g) is warming up to 80-85 ℃ with 100 parts commercial modified aliphatic amine epoxy curing agents, slowly adds 54 parts above-mentioned epoxy polyurethane prepolymer; After reacting 1 hour under this temperature; The UV light absorber UV-328 that adds 3 parts again stirred 0.5 hour, treat that UV light absorber dissolves fully after; Temperature of reaction is dropped to 60-80 ℃; The N that adds 19 parts at last, dinethylformamide, surveying the amine value is 203mgKOH/g.Pack after being cooled to room temperature, sealing is deposited.
3. the use of adhesive compound
By component A: B component is after 100: 100 weight ratio mix evenly forms the fluid of homogeneous it to be paved in the road surface, sheds colored aggregate through artificial or machine, guarantees that the latter covers on it fully, promptly forms versicolor color anti-skid road surface after the curing.
Performance by the tackiness agent of above-mentioned processing condition preparation is seen table 1.
Embodiment 2
1. the preparation of component A
100 parts E-44 epoxies tree is stirred under 60-80 ℃ temperature to the polypropylene glycol diglycidyl ether 6360 of fat with 15 parts, epoxy resin composition, testing epoxy equivalent (weight) is 223.Pack after being cooled to room temperature, sealing is deposited.
2. B component is synthetic
(1) dehydration of polyvalent alcohol: the polyoxytrimethylene ether glycol PPG-220 of capacity is dropped into have in the vacuum reaction still of stirring earlier, be heated to 120 ℃ under stirring, be evacuated to then-0.09mPa, dewatered 120 minutes, it is for use to be cooled to room temperature then.
(2) preparation of base polyurethane prepolymer for use as: with 100 parts 2; 4-diphenylmethanediisocyanate
3056 is put in another reaction kettle; Under nitrogen protection; Stirring is warming up to 60 ℃; Slowly add (1) set by step then and took off 400 parts of the PPG-220 polyoxytrimethylene ether glycol of water, feed rate is the best with temperature of reaction kettle at 80～85 ℃, wait to add polyoxytrimethylene ether glycol after; Continue reaction 4 hours, test NCO content is 3.36wt%.
(3) preparation of epoxy polyurethane prepolymer: with the E-51 epoxy resin of the base polyurethane prepolymer for use as of 100 parts above-mentioned steps (2) and 60 parts stirring reaction 4 hours under 80-85 ℃ of temperature; Surveying NCO content is 0%; Show that reaction accomplishes; The carbonic acid allyl ester that adds 100 parts again forms epoxy polyurethane resin prepolymer, and epoxy equivalent (weight) is 907.
(4) preparation of polyurethane-modified amine hardener: 30 parts two propylene triamines, 20 parts the mixture of polypropylene glycol diamine (trade(brand)name: DA-2000, number-average molecular weight Mn=2000) of trimethylhexamethylenediamine and 50 parts are warming up to 80-85 ℃, slowly add 60 parts above-mentioned epoxy polyurethane prepolymer; After reacting 1 hour under this temperature; The UV light absorber UV-320 that adds 3 parts again stirred 0.5 hour, treat that UV light absorber dissolves fully after; Temperature of reaction is dropped to 60-80 ℃; The DMAC N,N that adds 25 parts at last, surveying the amine value is 230mgKOH/g.Pack after being cooled to room temperature, sealing is deposited.
3. the use of adhesive compound
By component A: B component is after 100: 100 weight ratio mix evenly forms the fluid of homogeneous it to be paved in the road surface, sheds colored aggregate through artificial or machine, guarantees that the latter covers on it fully, promptly forms versicolor color anti-skid road surface after the curing.
Performance by the tackiness agent of above-mentioned processing condition preparation is seen table 1.
Embodiment 3
1. the preparation of component A
The polypropylene glycol diglycidyl ether PEGGE-400 of 100 parts E-51 epoxy resin and 20 parts is stirred under 60-80 ℃ temperature, epoxy resin composition, the test epoxy equivalent (weight) is 196.Pack after being cooled to room temperature, sealing is deposited.
2. B component is synthetic
(1) dehydration of polyvalent alcohol: the polyoxytrimethylene ether glycol PPG-2028 of capacity is dropped into have in the vacuum reaction still of stirring earlier, be heated to 120 ℃ under stirring, be evacuated to then-0.09mPa, dewatered 120 minutes, it is for use to be cooled to room temperature then.
(2) preparation of base polyurethane prepolymer for use as: with 100 parts 2; 4-diphenylmethanediisocyanate
3056 is put in another reaction kettle; Under nitrogen protection; Stirring is warming up to 60 ℃; Slowly add (1) set by step then and took off 800 parts of the PPG-2028 polyoxytrimethylene ether glycol of water, feed rate is the best with temperature of reaction kettle at 80～85 ℃, wait to add polyoxytrimethylene ether glycol after; Continue reaction 4 hours, test NCO content is 1.86%.
(3) preparation of epoxy polyurethane prepolymer: with the E-44 epoxy resin of the base polyurethane prepolymer for use as of 100 parts above-mentioned steps (2) and 60 parts stirring reaction 4 hours under 80-85 ℃ of temperature; Survey NCO and contain the most 0%; Show that reaction accomplishes; Phthalic acid two (just) monooctyl ester that adds 100 parts again forms the epoxy polyurethane prepolymer, and epoxy equivalent (weight) is 1032.
(4) preparation of polyurethane-modified amine hardener: 100 parts of P-Fs-diethylenetriamine condenses (trade(brand)name: T-31, amine value 420) is warming up to 80-85 ℃, slowly adds 65 parts above-mentioned epoxy polyurethane prepolymer; After 1 hour, add 3 parts UV light absorber UV-320 in reaction under this temperature again, stirred 0.5 hour; After treating that UV light absorber dissolves fully; Temperature of reaction is dropped to 60-80 ℃, add 25 parts N-N-methyl-2-2-pyrrolidone N-at last, surveying the amine value is 215mgKOH/g.Pack after being cooled to room temperature, sealing is deposited.
3. the use of adhesive compound
By component A: B component is after 100: 100 weight ratio mix evenly forms the fluid of homogeneous it to be paved in the road surface, sheds colored aggregate through artificial or machine, guarantees that the latter covers on it fully, promptly forms versicolor color anti-skid road surface after the curing.
Performance by the tackiness agent of above-mentioned processing condition preparation is seen table 1.
Embodiment 4
1. the preparation of component A
The polypropylene glycol diglycidyl ether PEGGE-400 of 100 parts E-51 epoxy resin and 20 parts is stirred under 60-80 ℃ temperature, epoxy resin composition, the test epoxy equivalent (weight) is 196.Pack after being cooled to room temperature, sealing is deposited.
2. B component is synthetic
(1) dehydration of polyvalent alcohol: the polyoxytrimethylene ether glycol PPG-220 of capacity is dropped into have in the vacuum reaction still of stirring earlier, be heated to 120 ℃ under stirring, be evacuated to then-0.09mPa, dewatered 120 minutes, it is for use to be cooled to room temperature then.
(2) preparation of base polyurethane prepolymer for use as: with 100 parts 2; 4-diphenylmethanediisocyanate
3056 is put in another reaction kettle; Under nitrogen protection; Stirring is warming up to 60 ℃; Slowly add (1) set by step then and took off 400 parts of the PPG-220 polyoxytrimethylene ether glycol of water, feed rate is the best with temperature of reaction kettle at 80～85 ℃, wait to add polyoxytrimethylene ether glycol after; Continue reaction 4 hours, test NCO content is 3.36wt%.
(3) preparation of epoxy polyurethane prepolymer: with the E-44 epoxy resin of the base polyurethane prepolymer for use as of 100 parts above-mentioned steps (2) and 60 parts stirring reaction 4 hours under 80-85 ℃ of temperature; Surveying NCO content is 0%; Show that reaction accomplishes; The carbonic acid allyl ester that adds 100 parts again forms the epoxy polyurethane prepolymer, and epoxy equivalent (weight) is 1032.
(4) preparation of polyurethane-modified amine hardener: (trade(brand)name: R-2253 amine value: mixture 320mgKOH/g) is warming up to 80-85 ℃ with 30 parts of diamino diphenyl sulfones and 70 parts of commercial modification cycloaliphatic amines epoxy solidifying agent; The above-mentioned epoxy polyurethane prepolymer that slowly adds 55 parts; After 1 hour, add 3 parts UV light absorber UV-320 in reaction under this temperature again, stirred 0.5 hour; After treating that UV light absorber dissolves fully; Temperature of reaction is dropped to 60-80 ℃, add 25 parts N-N-methyl-2-2-pyrrolidone N-at last, recording the amine value is 196mgKOH/g.Pack after being cooled to room temperature, sealing is deposited.
3. the use of adhesive compound
By component A: B component is after 100: 100 weight ratio mix evenly forms the fluid of homogeneous it to be paved in the road surface, sheds colored aggregate through artificial or machine, guarantees that the latter covers on it fully, promptly forms versicolor color anti-skid road surface after the curing.
Performance by the tackiness agent of above-mentioned processing condition preparation is seen table 1.
Table 1. color anti-skid road surface is with the performance index of polyurethane modified epoxy resin tackiness agent
Can find out by table 1, the ultimate tensile strength of various embodiments of the present invention all >=more than the 18.6mPa; Elongation at break >=48.6%; Ultimate compression strength >=12.5mPa; Gel time >=22min; Setting time >=120min; Shore A hardness >=86; Sliding resistance >=73 (high anti-slip type).This shows that color anti-skid road surface of the present invention satisfies the People's Republic of China's transportation industry standard of pavement antiskid paint fully with the polyurethane modified epoxy resin tackiness agent, has broad application prospects.
Through the check of national building materials test center, the assay of color anti-skid road surface project that wear-resisting glue is examined of the present invention meets the anti-skidding cold technical requirement that is coated with type in the JT/T712-2008 standard.
Though above invention is intended to realize the bonding of highway pavement and anti-skidding aggregate, the present invention undoubtedly can extend to other near field, and like the bonding of building leak stopping joint filling, Furniture panel etc., this is conspicuous for a person skilled in the art.Therefore, under thought of the present invention, those skilled in the art can make various changes to the present invention on this basis or revise, and should belong to scope of the present invention equally.
Claims (10)
1. polyurethane modified epoxy resin tackiness agent, it comprises component A and B component, wherein
Component A is an epoxy resin composition, and it comprises:
(i) 100 weight part oxirane values are the bisphenol A type epoxy resin of 0.41-0.58mol/100g;
(ii) 1-20 parts by weight average molecular weight is the polypropylene glycol diglycidyl ether of 100-1000, is used to regulate the viscosity of component A;
B component is polyurethane-modified amine hardener, and it comprises:
(i) organic polyamine of 100 weight parts;
This organic polyamine be selected from down the group at least a: fatty amine, cycloaliphatic amines, aromatic amine, modified amine epoxy curing agent or their mixture;
The (ii) epoxy polyurethane prepolymer of 40-70 weight part,
The bisphenol A type epoxy resin that this epoxy polyurethane prepolymer is 0.41-0.58mol/100g by the base polyurethane prepolymer for use as and the 40-70 weight part oxirane value of 100 weight parts adds the 80-120 weight part again after polyreaction softening agent mixes,
Wherein said base polyurethane prepolymer for use as by one or more diphenylmethanediisocyanates and one or more number-average molecular weights be the polyvalent alcohol of 1000-10000 by 100: the 200-2000 part by weight is through being polymerized, and its isocyano NCO content is 0.5-6wt%;
The (iii) UV light absorber of 0.5-5 weight part;
The (iv) solvent of the solubilized epoxy polyurethane prepolymer of 15-30 weight part is used to regulate the viscosity of B component,
Component A and B component are deposited with being separated, during use by component A: B component is that 100: 100 weight ratio is used.
2. tackiness agent according to claim 1 is characterized in that, the oxirane value of bisphenol A type epoxy resin described in the said component A is 0.48-0.56mol/100g.
3. tackiness agent according to claim 1 is characterized in that, the number-average molecular weight of said polypropylene glycol diglycidyl ether is 120-600.
4. tackiness agent according to claim 1; It is characterized in that; The said diphenylmethanediisocyanate that is used for the synthesis of polyurethane performed polymer in the said B component is be selected from down group at least a: 4; 4 '-diphenylmethanediisocyanate, 2,4-diphenylmethanediisocyanate, their mixture.
5. tackiness agent according to claim 1 is characterized in that, said bisphenol A type epoxy resin be selected from down the group at least a: epoxy resin E-44, E-51, epoxy resin E-55, their mixture.
6. tackiness agent according to claim 1; It is characterized in that said softening agent is to be selected from down at least a in the group: Witcizer 300, DOP, epoxy soybean oil, carbonic acid allyl ester, PX 208, two or more mixture in them.
7. tackiness agent according to claim 1 is characterized in that, said UV light absorber be selected from down the group at least a: UV-328, UV-320, their mixture.
8. a method for preparing according to each described tackiness agent in the claim 1 to 7 comprises the steps:
(1) preparation of component A:
The bisphenol A type epoxy resin of 100 weight parts and the polypropylene glycol diglycidyl ether of 1-20 weight part are stirred under 60-80 ℃ temperature, epoxy resin composition, epoxy equivalent (weight) is 160-260, packs after being cooled to room temperature, sealing is deposited;
(2) preparation of B component
1. prepare base polyurethane prepolymer for use as:
The polyvalent alcohol that took off water that with at least a number-average molecular weight of at least a diphenylmethanediisocyanate of 100 weight parts and 200-2000 weight part is 1000-10000 is 60-90 ℃ of reaction 1-4 hour down; Generate isocyanate-terminated performed polymer, isocyano NCO content is 0.5-6wt%;
2. prepare the epoxy polyurethane prepolymer
The above-mentioned base polyurethane prepolymer for use as of 100 weight parts and the bisphenol A type epoxy resin of 40-70 weight part were reacted 1-4 hour under 60-90 ℃ of temperature; When NCO content drops to 0%; The softening agent that adds the 80-120 weight part forms the epoxy polyurethane prepolymer, and epoxy equivalent (weight) is 800-1600;
3. prepare polyurethane-modified amine hardener
The organic polyamine of 100 weight parts is warming up to 80-100 ℃, slowly adds the above-mentioned epoxy polyurethane prepolymer of 40-70 weight part, after reacting 1-2 hour under this temperature; The UV light absorber that adds the 0.5-5 weight part again; Stirred 0.25-0.5 hour, guarantee that UV light absorber dissolves fully after, temperature of reaction is dropped to 60-80 ℃; Add the solvent adjustment viscosity of 15-30 weight part solubilized epoxy polyurethane prepolymer at last, the amine value is 180-280mgKOH/g.
According to each described tackiness agent in the claim 1 to 7 at anti-ways and in application.
10. application according to claim 9 is characterized in that said anti-skid surface is a color anti-skid road surface, will be used according to each described tackiness agent and colored aggregate in the claim 1 to 7 during construction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110135746.XA CN102796243B (en) | 2011-05-24 | 2011-05-24 | Polyurethane modified epoxy resin adhesive, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110135746.XA CN102796243B (en) | 2011-05-24 | 2011-05-24 | Polyurethane modified epoxy resin adhesive, and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102796243A true CN102796243A (en) | 2012-11-28 |
| CN102796243B CN102796243B (en) | 2014-05-28 |
Family
ID=47195567
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110135746.XA Active CN102796243B (en) | 2011-05-24 | 2011-05-24 | Polyurethane modified epoxy resin adhesive, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102796243B (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103964748A (en) * | 2014-04-10 | 2014-08-06 | 广东省建筑科学研究院 | Quick patching material for expansion joint and preparation method thereof |
| CN106365508A (en) * | 2016-08-29 | 2017-02-01 | 福州皇家地坪有限公司 | Epoxy color sand coating |
| CN110016321A (en) * | 2019-03-12 | 2019-07-16 | 长沙理工大学 | A kind of deck paving water-proof binding layer material and preparation method thereof |
| CN110683791A (en) * | 2019-09-18 | 2020-01-14 | 长安大学 | Super-silent pavement paving material and application |
| CN110776693A (en) * | 2019-11-05 | 2020-02-11 | 温州丰宝客科技有限公司 | High-heat-preservation environment-friendly packaging box material and preparation method thereof |
| CN112123499A (en) * | 2020-10-09 | 2020-12-25 | 北华大学 | Anti-corrosion shaving board and preparation method thereof |
| CN112831301A (en) * | 2020-12-31 | 2021-05-25 | 山西省交通科技研发有限公司 | High-light-reflection environment-friendly colorful anti-skid pavement and preparation method thereof |
| CN113896861A (en) * | 2021-11-26 | 2022-01-07 | 中航复合材料有限责任公司 | Dicyandiamide cured epoxy resin suitable for out-of-tank molding and preparation method thereof |
| CN114163901A (en) * | 2021-12-15 | 2022-03-11 | 上铁芜湖高新材料技术有限公司 | Epoxy polyurethane composite waterproof material for high-speed rail bridge and construction method thereof |
| CN116769277A (en) * | 2023-05-30 | 2023-09-19 | 江苏恒隆通新材料科技有限公司 | Medium-temperature fast-curing high-hardness laminated resin |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101348701A (en) * | 2008-09-12 | 2009-01-21 | 云南光电辅料有限公司 | Optical light color low stress modified epoxy adhesive and preparation of |
| US20090131605A1 (en) * | 2005-06-09 | 2009-05-21 | Adeka Corporation | Hardenable resin composition |
| CN101475788A (en) * | 2009-01-15 | 2009-07-08 | 湖南神力实业有限公司 | High strength polyurethane modified epoxy construction structure glue and manufacturing method thereof |
-
2011
- 2011-05-24 CN CN201110135746.XA patent/CN102796243B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20090131605A1 (en) * | 2005-06-09 | 2009-05-21 | Adeka Corporation | Hardenable resin composition |
| CN101348701A (en) * | 2008-09-12 | 2009-01-21 | 云南光电辅料有限公司 | Optical light color low stress modified epoxy adhesive and preparation of |
| CN101475788A (en) * | 2009-01-15 | 2009-07-08 | 湖南神力实业有限公司 | High strength polyurethane modified epoxy construction structure glue and manufacturing method thereof |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103964748A (en) * | 2014-04-10 | 2014-08-06 | 广东省建筑科学研究院 | Quick patching material for expansion joint and preparation method thereof |
| CN103964748B (en) * | 2014-04-10 | 2016-01-20 | 广东省建筑科学研究院集团股份有限公司 | A kind of expansion joint fast repairing material and preparation method thereof |
| CN106365508A (en) * | 2016-08-29 | 2017-02-01 | 福州皇家地坪有限公司 | Epoxy color sand coating |
| CN110016321A (en) * | 2019-03-12 | 2019-07-16 | 长沙理工大学 | A kind of deck paving water-proof binding layer material and preparation method thereof |
| CN110683791A (en) * | 2019-09-18 | 2020-01-14 | 长安大学 | Super-silent pavement paving material and application |
| CN110776693A (en) * | 2019-11-05 | 2020-02-11 | 温州丰宝客科技有限公司 | High-heat-preservation environment-friendly packaging box material and preparation method thereof |
| CN112123499A (en) * | 2020-10-09 | 2020-12-25 | 北华大学 | Anti-corrosion shaving board and preparation method thereof |
| CN112831301A (en) * | 2020-12-31 | 2021-05-25 | 山西省交通科技研发有限公司 | High-light-reflection environment-friendly colorful anti-skid pavement and preparation method thereof |
| CN112831301B (en) * | 2020-12-31 | 2023-04-07 | 山西省交通科技研发有限公司 | High-light-reflection environment-friendly colorful anti-skid pavement and preparation method thereof |
| CN113896861A (en) * | 2021-11-26 | 2022-01-07 | 中航复合材料有限责任公司 | Dicyandiamide cured epoxy resin suitable for out-of-tank molding and preparation method thereof |
| CN114163901A (en) * | 2021-12-15 | 2022-03-11 | 上铁芜湖高新材料技术有限公司 | Epoxy polyurethane composite waterproof material for high-speed rail bridge and construction method thereof |
| CN116769277A (en) * | 2023-05-30 | 2023-09-19 | 江苏恒隆通新材料科技有限公司 | Medium-temperature fast-curing high-hardness laminated resin |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102796243B (en) | 2014-05-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102796243B (en) | Polyurethane modified epoxy resin adhesive, and preparation method and application thereof | |
| CN107033611B (en) | High-grade asphalt composition with waterproof function and construction method using same | |
| CN102408860B (en) | Flexible epoxy adhesive and application | |
| CN109370463B (en) | Self-adhesive asphalt cement, preparation method thereof and crack sticker capable of being adhered to damp base surface and comprising self-adhesive asphalt cement | |
| CN101003688A (en) | High performance pavement material of epoxy asphalt, preparation method and application | |
| KR101515069B1 (en) | Method for pavement of road using epoxy concrete composition | |
| CN108219654A (en) | Polyurethane non-skid coating | |
| CN104927730A (en) | Graphene composite bonding material applied to pavements, graphene composite pavement and preparation method therefor | |
| JP2001072862A (en) | Asphalt composition, its production and use | |
| CN108329826B (en) | Two-component solvent-free polyurethane coating | |
| JP7107920B2 (en) | Polymer coated particles for polymer concrete compositions | |
| RU2268279C2 (en) | Rubber coating | |
| JP6193250B2 (en) | Repair method and repair kit to repair roads, passages and other places used for traffic | |
| US20080300351A1 (en) | Coloring binder for pavement of a road and method for producing the same | |
| JP2012510008A (en) | Recycling road paving materials | |
| JP3975336B2 (en) | Concrete stripping prevention method | |
| CN109722078A (en) | A kind of environment-protecting color roadway applications material and road markings laying method | |
| JP6841546B2 (en) | Floor slab pavement structure | |
| KR100936266B1 (en) | The color nonslip paving material for a road and the making method thereof and the paving method thereof | |
| CN114958184A (en) | Road surface anti-skid coating | |
| US20210355030A1 (en) | Adhesion Promoter Coated Particles for Polymer Concrete Compositions | |
| KR102191001B1 (en) | Adhesive Composition for Attaching a Road Marker | |
| KR102119732B1 (en) | Modified-Asphalt Concrete Compositions for Pavement of Roads Using Styrene Isoprene Styrene, Styrene Ethylene Butylene Styrene and Aggregate-powder of Improved Grain Size and Constructing Methods Using Thereof | |
| CN110982413A (en) | Road paint and preparation method and using method thereof | |
| KR102119751B1 (en) | High Grade Waterproofing Asphalt Concrete Composition Having Styrene Isoprene Styrene, Styrene Ethylene Butylene Styrene and Aggregate-powder of Improved Grain Size and Constructing Methods Using Thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C56 | Change in the name or address of the patentee | ||
| CP02 | Change in the address of a patent holder |
Address after: 201114 Shanghai, Minhang District Jin Jin Road, Lane 2049, room 38, No. 213 Patentee after: Heda Polymer Science and Technology Co., Ltd., Shanghai Address before: 201210 Shanghai city Pudong New Area Zhangjiang Town Sunqiao mianbei Road 58 Lane 99 Patentee before: Heda Polymer Science and Technology Co., Ltd., Shanghai |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20180515 Address after: No. 1188, No. 1188, three days door Road, Huzhou, Zhejiang Province, 5 Patentee after: Huzhou compound datu Hongxin Materials Technology Co., Ltd. Address before: 201114 room 213, 2049 lane, Pujin Road, Minhang District, Shanghai, 213. Patentee before: Heda Polymer Science and Technology Co., Ltd., Shanghai |