CN102634985B - Closed isocyanate adhesive for gumming fiber framework materials of rubber products, composition of closed isocyanate adhesive, preparation method and application - Google Patents
Closed isocyanate adhesive for gumming fiber framework materials of rubber products, composition of closed isocyanate adhesive, preparation method and application Download PDFInfo
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Abstract
The invention discloses closed isocyanate adhesive for gumming fiber framework materials of rubber products, a composition of the closed isocyanate adhesive, a preparation method and application, which belong to the technical field of closed isocyanate adhesive and preparation methods thereof. When the closed isocyanate adhesive is diluted by water until the content of solid accounts for 3% by weight, particles of the isocyanate adhesive are spherical, the diameters of 90% of the particles are smaller than 2 micrometers, and the average diameter of the particles is smaller than 1.5 micrometers. The preparation method includes that after being reacted with copolymer in organic solvent, isocyanate monomer is in polymerization closed reaction with a sealing agent compound; the isocyanate monomer is emulsified into homogenous emulsion after the reaction is finished; and then the organic solvent is removed, water is added in the homogenous emulsion so as to adjust the concentration of a product, and accordingly an adhesive dispersion product is obtained. The solid particles in the emulsion are spherical, the structure is stable, particle size distribution is narrower, particle sizes are small, the particles are more uniformly distributed on the surfaces of fiber fabrics, sediments are seldom formed during specific application, and the utilization quantity can be reduced by 20%.
Description
Technical field
The present invention relates to the technical field of a kind of blocked isocyanate adhesive and preparation method thereof, more particularly, relate to blocked isocyanate adhesive and composition and Preparation method and use that a kind of rubber fiber reinforcement material impregnation is used.
Background technology
In the production of rubber such as tire, adhesive tape, various fiber reinforcement materials are used for strengthening the intensity of rubber.Usually, these fibrous materials will be through surperficial dipping process to improve the bonding strength between itself and the rubber.Polyamide (nylon) fiber only need to be processed by Resorcin-Formaldehyde-Latex (RFL) system single bath process can obtain desirable bonding effect.Yet Polyester Fibers need to be carried out single bath process or two-bath process processing through add chlorophenol resin or blocked isocyanate in Resorcin-Formaldehyde-Latex (RFL) system usually again.Single bath process uses the mixture of chlorophenol or blocked isocyanate and RFL to carry out dipping process usually; And to obtain better bonding effect, and if usually use the two-bath process impregnation: first bath uses the composition of blocked isocyanate and soluble epoxide to carry out preliminary treatment, the second bath re-uses RFL and processes.
That above-mentioned blocked isocyanate generally uses in producing at present is the MDI(CAS54112-23-1 of caprolactam sealing), common manufacture craft is that the compound crystalline powder is scattered in the water in the presence of surfactant, the form of making aqueous dispersions through mechanical lapping provides, for example the CBI of Ma'an Mountain section English synthetic material Co., Ltd is serial, the grilbond IL6 of Switzerland EMS.This adhesive composition generally uses in the impregnation of polyester backbone material is produced at present, and has really obtained the stable level of adhesion of generally acknowledging.Yet, the intrinsic shortcoming of mechanical disintegration mode is that particle size distribution is wide, out-of-shape, irregular shape of particle and size are unfavorable for being distributed in uniformly adhesive surface, these have caused in use than being easier to form precipitation and cohesion, precipitation can reduce the utilization rate of active ingredient, and condensation product can adhere to the pollution impregnation equipment, shortens cleaning cycle.
Summary of the invention
1. invent the technical problem that will solve
Distribute wide for existing blocked isocyanate Diameter of Binder Particles, out-of-shape, in use form easily precipitation and cohesion, the low deficiency of utilization rate that causes active ingredient, the invention provides blocked isocyanate adhesive and composition and preparation method that a kind of rubber fiber reinforcement material impregnation is used, owing to adopted a kind of new emulsification preparation thereof, by controlled oligomerization, can obtain a kind of brand-new blocked isocyanate adhesive, when this adhesive was diluted with water to solid weight content and is 3%, its shape of particle was spheroidal.
2. technical scheme
For achieving the above object, technical scheme provided by the invention is:
The blocked isocyanate adhesive that a kind of rubber fiber reinforcement material impregnation of the present invention is used, this blocked isocyanate adhesive is when being diluted with water to solid weight content and being 3%, and its shape of particle is spheroidal.
Further, 90% described particle diameter is less than 2 μ m, and mean particle diameter is less than 1.5 μ m.
Further, in the infrared spectrogram of described blocked isocyanate adhesive, at 1410-1420cm
-1Interval place has characteristic absorption peak.
A kind of composition that contains above-mentioned blocked isocyanate adhesive of the present invention, said composition when being diluted with water to solid weight content and being 3%, wherein contains the particle of spheroidal; Its composition component comprises that above-mentioned weight percent content is the blocked isocyanate adhesive more than 10%, also comprises in other blocked isocyanate adhesives, epoxy resin, phenolic resins, synthetic latex, Heveatex, acrylic ester copolymer latex, vinyl acetate emulsion, the polystyrene emulsion one or more.
The preparation method of the blocked isocyanate adhesive that a kind of rubber fiber reinforcement material impregnation of the present invention is used the steps include:
(1) oligomer structure reaction: isocyanate-monomer is mixed with copolymer in organic solvent, wherein the weight of copolymer be isocyanate-monomer weight 0.01-2 doubly, this copolymer is: the material that the mixture of one or more in polyethylene glycol, polypropylene glycol, polytetramethylene glycol, PolyTHF, carboxylic acid or its salt, amino acid or its salt, polyester, the polyamide and copolymerization thereof produce;
(2) capping: after step (1) finishes, add sealer and carry out the polymerization capping, the amount of substance of the sealer that wherein adds is 0.5-2 times of isocyano equivalent in the isocyanate-monomer, and when treating that free isocyano weight percent content is lower than 1%, the polymerization capping finishes;
(3) emulsification: after step (2) finished, adding emulsifying agent and deionized water also stirred, and wherein, the weight of emulsifying agent is the 0-50% of step (2) product gross weight, and the addition of deionized water is calculated according to the product design that finally will reach and added; In this step, if when the copolymer that adds in the step (1) provided enough hydrophily, this step can not added new emulsifying agent, adopts the material that adds in the step (1) to use as reactive emulsifier, as: dihydromethyl propionic acid, polyethylene glycol.
(4) remove solvent: with the emulsion decompression vacuum pumping of step (3), distillation removes organic solvent, and the evaporative removal organic solvent that perhaps heats up namely obtains the blocked isocyanate adhesive that rubber fiber reinforcement material impregnation is used.This step is removed organic solvent, is in order to remove the smell of product, not affect the serviceability of final products, so should remove as much as possible organic solvent.
Further, step (4) adds water and regulates binder concn afterwards, obtains adhesive aqueous dispersions product, and wherein solids content is 1%-70%, perhaps above-mentioned emulsion is passed through drying, is processed into pulverous powder morphology adhesive.
Further, organic solvent described in the step (1) be not with the organic solvent of isocyanate-monomer reaction, this organic solvent is: the mixture of one or more materials in benzene,toluene,xylene, cyclohexane, halogenated hydrocarbons, solvent naphtha, dimethyl formamide, ethers, butanone, the acetone; Isocyanate-monomer described in the step (1) is: the mixture of one or more materials of thick MDI, methyl diphenylene diisocyanate, TDI or its dimer, HDI, NDI or IPDI.
Further, the sealer in the step (2) is: the mixture of one or more materials in lactams, phenols or the oximes; Emulsifying agent is nonionic or anion surfactant or its mixture in the step (3).Emulsifying agent of the present invention is organic sulfonic acid salt, organic carboxyl acid salt or polyethenoxy ether class.
Further, add catalyst in the step (1), this catalyst is base catalysis immunomodulator compounds, organo-metallic compound or organic phosphine compound, and the weight of its adding is less than 0.2 times of isocyanate-monomer weight.Preparation method of the present invention selects or does not select catalyst all can realize, uses if necessary catalyst, can use catalyst well known to those skilled in the art, for example the base catalysis immunomodulator compounds: organic amine, inorganic base; Organo-metallic compound: organotin, zinc acetate; Organic phosphine compound: aryl phosphine etc.
The purposes of a kind of above-mentioned blocked isocyanate adhesive of the present invention, in the dipping process of rubber with framework material polyester fiber and fabric thereof, join as additive and to carry out single bath process among the RFL and process, perhaps as one of the composition of first bath preliminary treatment glue in the two-bath process.
3. beneficial effect
Adopt technical scheme provided by the invention, compare with existing known technology, have following remarkable result:
(1) the blocked isocyanate adhesive among the present invention, the existence of its oligomer has reduced the crystallinity of product, blocked isocyanate adhesive of the present invention can directly be dispersed into uniform and stable emulsion under suitable surfactant system, with comparing that traditional mechanical lapping makes, solids are spheroidal in the emulsion, Stability Analysis of Structures, particle diameter distributes narrower, particle diameter is little, so that it is more even to distribute in fabric surface, show more outstanding bonding stripper surface, effectively improve and peel off the flaw that shows money or valuables one carries unintentionally, when concrete the application, almost do not precipitate, so that can reduce use amount 20%;
(2) because the oligomer of isocyanate-monomer self can be dissociated into original monomer under higher temperature, therefore also can regard a kind of enclosed construction as, because this enclosed construction does not need sealer to participate in, with the more isocyanates that can dissociate out under the aliquot, effective sharp utilization rate can be higher than traditional product;
(3) the adhesion pollution to equipment alleviates greatly in the impregnation production process, but the extension device cleaning cycle has improved utilization rate of equipment and installations.
Description of drawings
Fig. 1-1 is the particle diameter distribution map of adhesive C BI-LF among the Comparative Examples a;
Fig. 1-2 is the particle diameter distribution map of product grilbond IL6 among the Comparative Examples b;
Fig. 1-3 is the infrared spectrogram of adhesive C BI-LF among the Comparative Examples a;
Fig. 1-4 is the infrared spectrogram of product grilbond IL6 among the Comparative Examples b;
Fig. 1-5 is the microphotograph of adhesive C BI-LF among the Comparative Examples a;
Fig. 1-6 is the microphotograph of product grilbond IL6 among the Comparative Examples b;
Fig. 2 is the infrared spectrogram of adhesive among the embodiment 1;
Fig. 3 is the infrared spectrogram of adhesive among the embodiment 2;
Fig. 4 is the infrared spectrogram of adhesive among the embodiment 3;
Fig. 5 is the infrared spectrogram of adhesive among the embodiment 4;
Fig. 6 is the infrared spectrogram of adhesive among the embodiment 5;
Fig. 7 is the infrared spectrogram of adhesive among the embodiment 15;
Fig. 8 is the infrared spectrogram of adhesive among the embodiment 16;
Fig. 9 is the microphotograph of adhesive among the embodiment 1;
Figure 10 is the microphotograph of adhesive among the embodiment 2;
Figure 11 is the microphotograph of adhesive among the embodiment 3;
Figure 12 is the microphotograph of adhesive among the embodiment 4;
Figure 13 is the microphotograph of adhesive among the embodiment 5;
Figure 14 is the microphotograph of adhesive among the embodiment 15;
Figure 15 is the microphotograph of adhesive among the embodiment 16;
Figure 16 is the particle diameter distribution map of adhesive among the embodiment 1;
Figure 17 is the particle diameter distribution map of adhesive among the embodiment 2.
The specific embodiment
Be further to understand content of the present invention, the invention will be further described below in conjunction with embodiment, need to prove that these embodiment only are used for that the present invention will be described but not limit the scope of the invention.
Among the preparation method of the present invention, the isocyanate-monomer that uses is thick MDI, methyl diphenylene diisocyanate, TDI or its dimer, HDI, the mixture of one or more materials of NDI or IPDI, concrete material is as follows: diphenyl-methane-4,4-and/or-2,4-vulcabond (MDI), rough or purify MDI polymer (PMDI), other MDI isomers with all, for example: 3,4-MDI, 2,2-M D I, and/or 2,3-M D I, 2,2 of 4-and/or 2,6-toluene diisocyanate and oligomer thereof, particularly dimerization, the 4-toluene diisocyanate, 1-isocyanato--3-isocyanic acid methyl-3,5,5-trimethyl-cyclohexane (isophorone-vulcabond or IPDI), 1,6-hexylidene diisocyanate (HDI).The polyisocyanate of polyisocyanate adduct form for example, contains the isocyanuric acid ester of polyisocyanate, urea diketone, biuret, urethane vinegar, allophanate, carbodiimides, and/or the compound such as oxa-diazine.
Among the preparation method of the present invention, the sealer of selecting is the known sealer of those skilled in the art, comprising: the monobasic phenols, for example, phenol, resorcinol, first (benzene) phenol, pseudocuminol, tert-butyl phenol.Lactams, for example, epsilon-caprolactams, δ-valerolactam.Oximes, for example, methyl ethyl ketone oxime (diacetylmonoxime), methyl amyl ketoxime and cyclohexanone-oxime.One-level, secondary and tertiary alcohol class, gylcol ether easily forms the compound of enol, for example, acetoacetic ester, acetylacetone,2,4-pentanedione, malonate derivative.The secondary aromatic amine, acid imide, thio-alcohol, triazole type.During concrete the use, can make the mixture of one or more materials wherein.
Below detecting particle diameter in the experiment adopts the laser particle size diffractometer to disperse take pure water as the medium wet method to detect; Infrared spectrum adopts Fourier infrared spectrograph; Electron microscopy is that adhesive is diluted with water to 3% solid content, obtains microphoto through electron microscope.
Comparative Examples
Comparative Examples a: the products with adhesive agent on sale CBI-LF of English synthetic material Co., Ltd of Ma'an Mountain section, particle diameter distribution map and analysis result are seen Fig. 1-1, the particle diameter D10-D90 of particle is distributed between the 0.57-3.50 micron, and infrared spectrogram is seen Fig. 1-3, and microphoto is seen Fig. 1-5.
Comparative Examples b: Switzerland EMS product grilbond IL6, particle diameter distribution map and analysis result are seen Fig. 1-2, and particle diameter D10-D90 is distributed between the 0.61-3.79 micron, and infrared spectrogram is seen Fig. 1-4, and microphoto is seen Fig. 1-6.
Infrared spectrogram among upper Comparative Examples a and the Comparative Examples b is showed no 1410-1420 cm
-1Obvious absorption peaks is arranged, and microphoto shows that particulate form is irregular fragment, and the particle diameter wider distribution.
Agitator is housed, thermometer, add acetone 170g in the round-bottomed flask of vacuum system, methyl diphenylene diisocyanate (MDI100 that Yantai Wanhua Polyurethane Co., Ltd produces) 170g, polyethylene glycol 20g, be warming up to 60 ℃, stirring reaction 2 hours, add caprolactam 150g, 60 ℃ are continued reaction and are lower than 1% until sampling detects free isocyano-content, be down to normal temperature, add emulsifying agent dioctyl succinate sodium sulfonate 10g, stir the lower deionized water 500g that slowly adds, be emulsified into homogeneous latex emulsion, decompression vacuum pumping distillation desolvation acetone, adding deionized water adjusting solids content is 40% again, obtains the blocked isocyanate adhesive of emulsion form.
Analyze after testing, average grain diameter is 0.70 micron, and above-mentioned particle diameter D10-D90 is 0.4-1.01 μ m, and particle diameter distribution map and analysis result are seen Figure 16; Infrared spectrogram is seen Fig. 2, shows wavelength 1413 cm
-1Obvious absorption peaks is arranged, the blocked isocyanate adhesive that present embodiment makes, when being diluted with water to solid weight content and being 3%, microphotograph is seen Fig. 9, its solia particle is spheroidal.Solids are spheroidal in the emulsion of present embodiment, Stability Analysis of Structures, particle diameter distributes narrower, particle diameter is little, so that it is more even to distribute in fabric surface, show more outstanding bonding stripper surface, effectively improve and peel off the flaw that shows money or valuables one carries unintentionally, when concrete the application, almost do not precipitate, so that can reduce use amount about 20%.
Embodiment 2
Agitator is housed, thermometer, add acetone 170g in the round-bottomed flask of vacuum system, the PM100 that thick MDI(Yantai Wanhua Polyurethane Co., Ltd produces) 170g, polyethylene glycol 20g, be warming up to 60 ℃, stirring reaction 2 hours, add caprolactam 135g, 60 ℃ are continued reaction and are lower than 1% until sampling detects free isocyano-content, be down to normal temperature, add dioctyl succinate sodium sulfonate 10g, stir the lower deionized water 500g that slowly adds, be emulsified into homogeneous latex emulsion, decompression vacuum pumping distillation desolvation acetone, adding deionized water adjusting solids content is 40% again, obtains the blocked isocyanate adhesive of emulsion form.This adhesive can be used as one of component of first bath dipping solution in the polyester cord two-bath process, perhaps adds as bonding active additive and carries out the single bath process processing in the RFL glue.
Analyze after testing, average grain diameter is 0.69 micron, and described particle diameter D10-D90 is 0.39-1.00 μ m, and particle diameter distribution map and analysis result are seen Figure 17; Infrared spectrogram is seen Fig. 3, shows wavelength 1413 cm
-1Obvious absorption peaks is arranged, the blocked isocyanate adhesive that present embodiment makes, when being diluted with water to solid weight content and being 3%, microphotograph is seen Figure 10, its solia particle is spheroidal.
Agitator is housed, thermometer, add acetone 170g in the round-bottomed flask of vacuum system, methyl diphenylene diisocyanate (MDI100 that Yantai Wanhua Polyurethane Co., Ltd produces) 170g, polyethylene glycol 20g, catalyst of triethylamine 0.5g, be warming up to 60 ℃, stirring reaction 1 hour, add caprolactam 150g, reaction is lower than 1% until sampling detects free isocyano-content, be down to normal temperature, add dioctyl succinate sodium sulfonate 10g, stir the lower deionized water 500g that slowly adds, be emulsified into homogeneous latex emulsion, decompression vacuum pumping distillation desolvation acetone, adding deionized water adjusting solids content is 40% again, obtains the blocked isocyanate adhesive of emulsion form.
Catalyst has been adopted in oligomer structure reaction in the present embodiment, can improve reaction speed, among the preparation method of blocked isocyanate adhesive of the present invention, select or do not select catalyst all can realize, as select catalyst, can use catalyst well known to those skilled in the art, for example, base catalysis immunomodulator compounds: organic amine, inorganic base; Organo-metallic compound: organotin, zinc acetate; Organic phosphine compound: aryl phosphine etc.
Analyze after testing, average grain diameter is less than 1.5 microns, and infrared spectrogram is seen Fig. 4, shows wavelength 1413 cm
-1Characteristic absorption peak is arranged, the blocked isocyanate adhesive that present embodiment makes, when being diluted with water to solid weight content and being 3%, microphotograph is seen Figure 11, its solia particle is spheroidal.
Agitator is housed, thermometer, add acetone 170g in the round-bottomed flask of vacuum system, methyl diphenylene diisocyanate (MDI100 that Yantai Wanhua Polyurethane Co., Ltd produces) 170g, polyethylene glycol 20g, be warming up to 60 ℃, stirring reaction 2 hours, add diacetylmonoxime 115g, reaction is lower than 1% until sampling detects free isocyano-content, be down to normal temperature, add dioctyl succinate sodium sulfonate 10g, stir the lower deionized water 500g that slowly adds, be emulsified into homogeneous latex emulsion, decompression vacuum pumping distillation desolvation acetone, adding deionized water adjusting solids content is 40% again, obtains the blocked isocyanate adhesive of emulsion form.
Analyze after testing, average grain diameter is less than 1.5 microns, and infrared spectrogram is seen Fig. 5, shows wavelength 1414 cm
-1Obvious absorption peaks is arranged, the blocked isocyanate adhesive that present embodiment makes, when being diluted with water to solid weight content and being 3%, microphotograph is seen Figure 12, its solia particle is spheroidal.
Agitator is housed, thermometer, add acetone 170g in the round-bottomed flask of vacuum system, methyl diphenylene diisocyanate (MDI100 that Yantai Wanhua Polyurethane Co., Ltd produces) 170g, polyethylene glycol 20g, catalyst of triethylamine 0.5g, be warming up to 60 ℃, stirring reaction 2 hours, add phenol 125g, reaction is lower than 1% until sampling detects free isocyano-content, be down to normal temperature, add dioctyl succinate sodium sulfonate 5g, polyoxyethylene nonylphenol ether 5g stirs the lower deionized water 500g that slowly adds, be emulsified into homogeneous latex emulsion, decompression vacuum pumping distillation desolvation acetone, adding deionized water adjusting solids content is 40% again, obtains the blocked isocyanate adhesive of emulsion form.
Analyze after testing, average grain diameter is less than 1.5 microns, and infrared spectrogram is seen Fig. 6, shows wavelength 1412 cm
-1There is strong absworption peak at the place, the blocked isocyanate adhesive that present embodiment makes, and when being diluted with water to solid weight content and being 3%, microphotograph is seen Figure 13, its solia particle is spheroidal.
Embodiment 6
Agitator is housed, thermometer, add acetone 170g in the round-bottomed flask of vacuum system, methyl diphenylene diisocyanate (MDI100 that Yantai Wanhua Polyurethane Co., Ltd produces) 170g, polyethylene glycol 20g, be warming up to 60 ℃, stirring reaction 2 hours, add caprolactam 80g, 60 ℃ are continued reaction and are lower than 1% until sampling detects free isocyano-content, be down to normal temperature, add emulsifying agent dioctyl succinate sodium sulfonate 10g, stir the lower deionized water 500g that slowly adds, be emulsified into homogeneous latex emulsion, decompression vacuum pumping distillation desolvation acetone, adding deionized water adjusting solids content is 50% again, obtains the blocked isocyanate adhesive of emulsion form.
Analyze after testing, average grain diameter is less than 1.5 microns, the blocked isocyanate adhesive that present embodiment makes, and when being diluted with water to solid weight content and being 3%, microphotograph shows that solia particle is spheroidal.
Agitator is housed, thermometer, add acetone 170g in the round-bottomed flask of vacuum system, methyl diphenylene diisocyanate (MDI100 that Yantai Wanhua Polyurethane Co., Ltd produces) 170g, polyethylene glycol 20g, be warming up to 60 ℃, stirring reaction 2 hours, add caprolactam 300g, 60 ℃ are continued reaction and are lower than 1% until sampling detects free isocyano-content, be down to normal temperature, add emulsifying agent dioctyl succinate sodium sulfonate 10g, stir the lower deionized water 500g that slowly adds, be emulsified into homogeneous latex emulsion, heat up and evaporate desolvation acetone, adding deionized water adjusting solids content is 70% again, obtains the blocked isocyanate adhesive of emulsion form.
Analyze after testing, average grain diameter is less than 1.5 microns, the blocked isocyanate adhesive that present embodiment makes, and when being diluted with water to solid weight content and being 3%, microphotograph shows that solia particle is spheroidal.
Be equipped with and add dimethyl formamide 100g in the round-bottomed flask of agitator, thermometer, vacuum system, methyl diphenylene diisocyanate (MDI100 that Yantai Wanhua Polyurethane Co., Ltd produces) 100g, dihydromethyl propionic acid 15g, under 50-60 ℃ of condition, stirring reaction 30 minutes, add polyethylene glycol 30g, continue reaction 30 minutes, add diacetylmonoxime 35g, reaction is lower than 1% until sampling detects free isocyano-content, add 2.5% sodium hydrate aqueous solution 200g, be emulsified into homogeneous latex emulsion.
Analyze after testing, average grain diameter is less than 1.5 microns, the blocked isocyanate adhesive that present embodiment makes, and when being diluted with water to solid weight content and being 3%, microphotograph shows that solia particle is spheroidal.
Be equipped with and add dimethyl formamide 100g in the round-bottomed flask of agitator, thermometer, vacuum system, methyl diphenylene diisocyanate (MDI100 that Yantai Wanhua Polyurethane Co., Ltd produces) 100g, dihydromethyl propionic acid 15g, under 50-60 ℃ of condition, stirring reaction 30 minutes, add polyethylene glycol 30g, continue reaction 30 minutes, add diacetylmonoxime 35g, reaction is lower than 1% until sampling detects free isocyano-content, add triethylamine 20g, deionized water 200g is emulsified into homogeneous latex emulsion.
Analyze after testing, average grain diameter is less than 1.5 microns, the blocked isocyanate adhesive that present embodiment makes, and when being diluted with water to solid weight content and being 3%, microphotograph shows that solia particle is spheroidal.
Be equipped with and add acetone 100g in the round-bottomed flask of agitator, thermometer, vacuum system, methyl diphenylene diisocyanate (MDI100 that Yantai Wanhua Polyurethane Co., Ltd produces) 60g, polyester diol (Yantai China prosperous polyurethane Co., Ltd 1024) 100g, under 60 ℃ of conditions, stirring reaction 3 hours, adding is as the polyethylene glycol 20g of copolymer, caprolactam 35g, reaction is lower than 1% until sampling detects free isocyano-content, add dioctyl succinate sodium sulfonate 10g, deionized water 350ml is emulsified into homogeneous latex emulsion.Decompression vacuum pumping distillation desolvation acetone, adding deionized water adjusting solids content is 40% again, obtains the blocked isocyanate adhesive of emulsion form.
Analyze after testing, average grain diameter is less than 1.5 microns, the blocked isocyanate adhesive that present embodiment makes, and when being diluted with water to solid weight content and being 3%, microphotograph shows that solia particle is spheroidal.
In the present embodiment, in epoxy resin (JF45 of Wuxi resin processing plant) 100g, add acetone 100g and be dissolved into epoxy resin solution.
Agitator is housed, thermometer, add acetone 100g in the round-bottomed flask of vacuum system, methyl diphenylene diisocyanate (MDI100 that Yantai Wanhua Polyurethane Co., Ltd produces) 100g, polyethylene glycol 15g, triethylamine 0.2g, be warming up to 60 ℃, stirring reaction 1.5 hours, add caprolactam 85g, reaction is lower than 1% until sampling detects free isocyano-content, adding above-mentioned epoxy resin solution stirs, add dioctyl succinate sodium sulfonate 10g, stir the lower deionized water 500g that slowly adds, be emulsified into homogeneous latex emulsion, decompression vacuum pumping distillation desolvation acetone, adding deionized water adjusting solids content is 40% again, obtains the blocked isocyanate adhesive of emulsion form.
Analyze after testing, average grain diameter is less than 1.5 microns, the blocked isocyanate adhesive that present embodiment makes, and when being diluted with water to solid weight content and being 3%, microphotograph shows that solia particle is spheroidal.
In the present embodiment, at phenolic resins (RF of Changzhou Shuguang Chemical Factory resin) 100g, add acetone 100g and be dissolved into phenol resin solution.
Agitator is housed, thermometer, add acetone 100g in the round-bottomed flask of vacuum system, methyl diphenylene diisocyanate (MDI100 that Yantai Wanhua Polyurethane Co., Ltd produces) 100g, polyethylene glycol 15g, triethylamine 0.2g, be warming up to 60 ℃, stirring reaction 1 hour, add caprolactam 85g, reaction is lower than 1% until sampling detects free isocyano-content, adding above-mentioned phenol resin solution stirs, add dioctyl succinate sodium sulfonate 10g, stir the lower deionized water 500g that slowly adds, be emulsified into homogeneous latex emulsion, decompression vacuum pumping distillation desolvation acetone, adding deionized water adjusting solids content is 40% again, obtains the blocked isocyanate adhesive of emulsion form.
Analyze after testing, average grain diameter is less than 1.5 microns, the blocked isocyanate adhesive that present embodiment makes, and when being diluted with water to solid weight content and being 3%, microphotograph shows that solia particle is spheroidal.
Embodiment 13
The processing step of present embodiment is with embodiment 1, and difference is: copolymer adopts polypropylene glycol, polytetramethylene glycol and PolyTHF, gets altogether 40g; Organic solvent adopts benzene, toluene and dimethylbenzene, gets altogether 170g; Isocyanate-monomer adopts HDI and NDI, gets altogether 170g, and proportioning is with embodiment 1, emulsification and remove solvent after, above-mentioned emulsion by dry, is processed into pulverous powder morphology adhesive.
Analyze after testing, average grain diameter is less than 1.5 microns, the blocked isocyanate adhesive that present embodiment makes, and when being diluted with water to solid weight content and being 3%, microphotograph shows that solia particle is spheroidal.
The processing step of present embodiment is with embodiment 1, difference is: copolymer adopts polytetramethylene glycol 2 g, organic solvent adopts cyclohexane 150g, isocyanate-monomer adopts IPDI170g, emulsification and remove solvent after, adding deionized water adjusting solids content is 1% again, obtains the blocked isocyanate adhesive of emulsion form.
Analyze after testing, average grain diameter is less than 1.5 microns, the blocked isocyanate adhesive that present embodiment makes, and when its solid weight content was 3%, microphotograph showed that solia particle is spheroidal.
With the sample 500g of embodiment 1 preparation, add CBI-LF(solid content 50%) 500g, stirring makes aggregate sample, solid content 45%.The adhesive for preparing among the embodiment 1 can mix with other blocked isocyanate adhesives of the prior art, the blocked isocyanate adhesive that these other blocked isocyanate adhesives refer to adopt the mode of mechanical disintegration commonly used in the prior art to prepare.
Analyze after testing, infrared spectrogram is seen Fig. 7, shows wavelength 1413 cm
-1There is strong absworption peak at the place, and microphotograph is seen Figure 14, and solia particle is fragment and spherical mixed distribution.Contain the spheroidal solids in the emulsion of present embodiment, Stability Analysis of Structures, particle diameter is little, so that it is more even to distribute in fabric surface, shows more outstanding bonding stripper surface, has effectively improved and has peeled off the flaw that shows money or valuables one carries unintentionally.
With the sample 500g of embodiment 2 preparations, add CBI-LF(solid content 50%) 500g, stirring makes aggregate sample, solid content 45%.
Analyze after testing, infrared spectrogram is seen Fig. 8, shows wavelength 1413 cm
-1There is absworption peak at the place, and microphotograph is seen Figure 15, and solia particle is fragment and spherical mixed distribution.
With the sample 500g of embodiment 1 preparation, add epoxy resin latex (E44 of Zhejiang Anbang New Material Development Co., Ltd. emulsion, solid content 40%) 200g, stirring makes aggregate sample, solid content 40%.
Analyze after testing, the composition of the blocked isocyanate adhesive that present embodiment makes when being diluted with water to solid weight content and being 3%, wherein contains the particle of spheroidal.The composition of this adhesive can be used for polyester cord first bath impregnation component, perhaps adds in the RFL glue as bonding active additive.
The sample 100g of embodiment 1 preparation is diluted with water to solid content 20%, adds chlorophenol resorcinol formaldehyde copolymer resins resin ammonia spirit (the good Xinghua RP of factory in Yixing, solid content 20%) 400g, stirring makes aggregate sample, solid content 20%.
Analyze after testing, the composition of the blocked isocyanate adhesive that present embodiment makes when being diluted with water to solid weight content and being 3%, wherein contains the particle of spheroidal.This composite adhesive can be used for polyester cord first bath impregnation component, perhaps adds in the RFL glue as bonding active additive.
Embodiment 19
With the sample 500g of embodiment 14 preparation, add butadiene-vinylpyridine copylymer latex (Zibo make a concerted effort chemical industry produce solid content 40%) 150g, stirring makes aggregate sample, solid content 10%.
Analyze after testing, the composition of the blocked isocyanate adhesive that present embodiment makes when being diluted with water to solid weight content and being 3%, wherein contains the particle of spheroidal.This composite adhesive can be used for polyester cord first bath impregnation component, can produce comparatively soft cord fabric feel.
Present embodiment adopts vinyl acetate emulsion and synthetic latex to mix with the adhesive that embodiment 1 prepares, and obtains solid content and be 25% aggregate sample.
Analyze after testing, the composition of the blocked isocyanate adhesive that present embodiment makes when being diluted with water to solid weight content and being 3%, wherein contains the particle of spheroidal.
The material that mixes with blocked isocyanate adhesive of the present invention can be: other blocked isocyanate adhesives (the blocked isocyanate adhesive that the Mechanical Crushing method prepares), epoxy resin, phenolic resins, synthetic latex, Heveatex, acrylic ester copolymer latex, the vinyl acetate emulsion, in the polystyrene emulsion one or more, mixed composition, when being diluted with water to solid weight content and being 3%, the particle that wherein all contains spheroidal, the solids of spheroidal in this emulsion, Stability Analysis of Structures, so that distribute more even in fabric surface, show more outstanding bonding stripper surface, effectively improve and peel off the flaw that shows money or valuables one carries unintentionally, when concrete the application, effectively reduced precipitation.
Serviceability test experiments one:
Above-described embodiment 1,4,15 samples are carried out the bond properties test, impregnation adopts the two-bath process impregnation, first bath adopts sealing than the mixed aqueous solution dipped cord of isocyanates and aqueous epoxy resins, after drying, the heat treatment, again with 20%RFL liquid dipping, drying, heat treatment obtain the impregnation cord fabric thread, and bond properties detects and adopts the GB/T2942-2009 method to detect the H-extraction.Concrete data see the following form 1, and that wherein Comparative Examples a adopts is the products with adhesive agent on sale CBI-LF of English synthetic material Co., Ltd of Ma'an Mountain section.
Used water-base epoxy is the product E P303 of English synthetic material Co., Ltd of Ma'an Mountain section in the table; Listed content is actual solids content (dry weight) in the table, and nonaqueous emulsion content (weight in wet base); Testing used cord fabric thread is 1670/2 of Taiji Ind Co., Ltd., Wuxi City's production.
The concrete data statistic of table 1 serviceability test one
Above result shows that adhesive composition of the present invention and Comparative Examples practical application contrast in the situation that has lowered actual use amount, still can reach similar bonding effect.
Serviceability test experiments two:
Above-described embodiment 1,4,15 samples are carried out the bond properties test, impregnation adopts the two-bath process impregnation, first bath adopts sealing than the mixed aqueous solution dipped cord of isocyanates and aqueous epoxy resins, after drying, the heat treatment, again with 20%RFL liquid dipping, drying, heat treatment obtain the impregnation cord fabric thread, and bond properties detects and adopts the GB/T2942-2009 method to detect the H-extraction.Concrete data see the following form 2, and that wherein Comparative Examples a adopts is the products with adhesive agent on sale CBI-LF of English synthetic material Co., Ltd of Ma'an Mountain section.
Used water-base epoxy is the product E P303 of English synthetic material Co., Ltd of Ma'an Mountain section in the table; Listed content is actual solids content (dry weight) in the table, and nonaqueous emulsion content (weight in wet base); Testing used cord fabric thread is 1670/2 of Taiji Ind Co., Ltd., Wuxi City's production.
The concrete data statistic of table 2 serviceability test two
Above result shows, adhesive composition of the present invention and Comparative Examples practical application contrast in the situation of equal actual use amount, reduce heat treatment draw zone temperature, still can reach similar bonding effect.
Claims (8)
1. blocked isocyanate adhesive that rubber fiber reinforcement material impregnation is used is characterized in that: this blocked isocyanate adhesive is when being diluted with water to solid weight content and being 3%, and its shape of particle is spheroidal; 90% described particle diameter is less than 2 μ m, and mean particle diameter is less than 1.5 μ m; In the infrared spectrogram of described blocked isocyanate adhesive, at 1410-1420cm
-1Interval place has characteristic absorption peak.
2. composition that contains blocked isocyanate adhesive claimed in claim 1 is characterized in that: said composition, when being diluted with water to solid weight content and being 3%, wherein contain the particle of spheroidal; Its composition component comprises that weight percent content claimed in claim 1 is the blocked isocyanate adhesive more than 10%, also comprises in other blocked isocyanate adhesives, epoxy resin, phenolic resins, synthetic latex, Heveatex, acrylic ester copolymer latex, vinyl acetate emulsion, the polystyrene emulsion one or more.
3. the preparation method of the blocked isocyanate adhesive used of a rubber fiber reinforcement material impregnation the steps include:
(1) oligomer structure reaction: isocyanate-monomer is mixed with copolymer in organic solvent, wherein the weight of copolymer be isocyanate-monomer weight 0.01-2 doubly, this copolymer is: the material that the mixture of one or more in polyethylene glycol, polypropylene glycol, polytetramethylene glycol, PolyTHF, carboxylic acid or its salt, amino acid or its salt, polyester, the polyamide and copolymerization thereof produce;
(2) capping: after step (1) finishes, add sealer and carry out the polymerization capping, the amount of substance of the sealer that wherein adds is 0.5-2 times of isocyano equivalent in the isocyanate-monomer, and when treating that free isocyano weight percent content is lower than 1%, the polymerization capping finishes;
(3) emulsification: after step (2) finished, adding emulsifying agent and deionized water also stirred, and wherein, the weight of emulsifying agent is the 0-50% of step (2) product gross weight, and the addition of deionized water is calculated according to the product design that finally will reach and added;
(4) remove solvent: with the emulsion decompression vacuum pumping of step (3), distillation removes organic solvent, and the evaporative removal organic solvent that perhaps heats up namely obtains the blocked isocyanate adhesive that rubber fiber reinforcement material impregnation is used.
4. the preparation method of the blocked isocyanate adhesive used of a kind of rubber fiber reinforcement material impregnation according to claim 3, it is characterized in that: step (4) afterwards, add water and regulate binder concn, obtain adhesive aqueous dispersions product, wherein solids content is 1%-70%, perhaps above-mentioned emulsion is passed through drying, be processed into pulverous powder morphology adhesive.
5. the preparation method of the blocked isocyanate adhesive used of a kind of rubber fiber reinforcement material impregnation according to claim 4, it is characterized in that: the organic solvent described in the step (1) for not with the organic solvent of isocyanate-monomer reaction, this organic solvent is: the mixture of one or more materials in benzene,toluene,xylene, cyclohexane, halogenated hydrocarbons, solvent naphtha, dimethyl formamide, ethers, butanone, the acetone; Isocyanate-monomer described in the step (1) is: the mixture of one or more materials of thick MDI, methyl diphenylene diisocyanate, TDI or its dimer, HDI, NDI or IPDI.
6. the preparation method of the blocked isocyanate adhesive used of a kind of rubber fiber reinforcement material impregnation according to claim 5, it is characterized in that: the sealer in the step (2) is: the mixture of one or more materials in lactams, phenols or the oximes; Emulsifying agent is nonionic or anion surfactant or its mixture in the step (3).
7. the preparation method of the blocked isocyanate adhesive that each described a kind of rubber fiber reinforcement material impregnation is used according to claim 3 ~ 6, it is characterized in that: add catalyst in the step (1), this catalyst is base catalysis immunomodulator compounds, organo-metallic compound or organic phosphine compound, and the weight of its adding is less than 0.2 times of isocyanate-monomer weight.
8. the purposes of the blocked isocyanate adhesive described in the claim 1, in the dipping process of rubber with framework material polyester fiber and fabric thereof, join as additive and to carry out single bath process among the RFL and process, perhaps as one of the composition of first bath preliminary treatment glue in the two-bath process.
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| CN103061124A (en) * | 2012-12-10 | 2013-04-24 | 东营市龙力得新材料有限公司 | Process for improving adhesion of polyester cord in impregnation process |
| CN103665493B (en) * | 2013-11-08 | 2016-03-02 | 浙江鸿腾橡胶有限公司 | For dipping solution and preparation method thereof and impregnated fabric and preparation method thereof of transmission belt |
| CN103602305B (en) * | 2013-11-18 | 2015-08-19 | 东北林业大学 | The preparation method of single-component water-based macromolecule-isocyanate composite adhesive and using method thereof |
| CN104404765B (en) * | 2014-12-18 | 2018-01-26 | 江苏久瑞高能电子有限公司 | A kind of aramid fiber cord fabric dipping glue, preparation method and impregnation aramid fiber cord fabric |
| CN105368131A (en) * | 2015-11-19 | 2016-03-02 | 佛山市新榜包装材料有限公司 | PVC protective film table printing ink binder additive |
| CN106084362B (en) * | 2016-06-28 | 2018-04-24 | 江苏太极实业新材料有限公司 | A kind of environmentally friendly fibre framework materials dipping solution and gum dipping process |
| CN108373528A (en) * | 2017-02-01 | 2018-08-07 | 胡海东 | A kind of composite matrix resin |
| CN108004784A (en) * | 2017-12-14 | 2018-05-08 | 芜湖华烨新材料有限公司 | A kind of dipping solution for improving Polyester Cord quality and preparation method thereof |
| CN109371683B (en) * | 2018-08-14 | 2024-10-18 | 江志平 | Fiber framework gum dipping material for rubber products and preparation and use methods thereof |
| CN109097993A (en) * | 2018-09-10 | 2018-12-28 | 江苏太极实业新材料有限公司 | A kind of fibre framework materials dipping solution |
| CN113943545B (en) * | 2021-09-26 | 2023-04-25 | 马鞍山科英合成材料有限公司 | Adhesive, composition, aqueous dispersion, dipping solution for dipping and application thereof |
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| DE10160570A1 (en) * | 2001-12-10 | 2003-06-18 | Bayer Ag | A single component PUR binder containing cycloaliphatic polyisocyanate enamel, isocyanate group blocking agent, polymeric OH component useful for production of stoving enamels by coil coating processes |
| JP2007505228A (en) * | 2003-09-12 | 2007-03-08 | テイジン・トゥワロン・ビー．ブイ． | Two-stage method for impregnating synthetic fibers |
| EP1757726A4 (en) * | 2004-05-18 | 2008-04-16 | Toyo Boseki | Reinforcement polyester cords for rubbers and process for production thereof |
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