CN102643623A - Polyurethane resin potting adhesive with high bonding strength and preparation method thereof - Google Patents
Polyurethane resin potting adhesive with high bonding strength and preparation method thereof Download PDFInfo
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- CN102643623A CN102643623A CN2012100972485A CN201210097248A CN102643623A CN 102643623 A CN102643623 A CN 102643623A CN 2012100972485 A CN2012100972485 A CN 2012100972485A CN 201210097248 A CN201210097248 A CN 201210097248A CN 102643623 A CN102643623 A CN 102643623A
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Abstract
The invention discloses a polyurethane resin potting adhesive with a high bonding strength, which is composed of a component A and a component B. The component A comprises castor oil and polyether polyatomic alcohol in parts by weight; the component B comprises hydroxyl-terminated polybutadiene, MDI (diphenylmethane diisocyanate), an accelerating agent and an additive; the molar ratio of hydroxyls of the hydroxyl-terminated polybutadiene to isocyanate radicals of the MDI is 0.06-0.25; and the MDI contains no less than 80 wt% of 4,4'-MDI and residues of isomerism homologues of the MDI or the modified MDI which contains no less than 80 wt% of the 4,4'-MDI isomer. The polyurethane resin potting adhesive disclosed by the invention has the high bonding strength and particularly has good bonding performance with plastic materials (PA66) including nylon and the like; and the polyurethane resin potting adhesive has good electric performance, lower inner stress and excellent heat impact resistance and is particularly suitable for potting and packaging electronic elements which have more demanding requirements on the inner stress, such as a reversing radar, a tire pressure monitor and the like.
Description
Technical field
The present invention relates to a kind of high bond strength urethane resin joint sealant and preparation method thereof, be applicable to embedding, seal electronics and electric component.
Background technology
Now, increasing electronics, electric component are applied on the automobile, make automobile convert the electronics synthesis body into from the conglomerate of pure mechanical part, with comfortableness, the security of continuous lifting driving.These electronics, electric component generally are equipped with electrical elements such as electronic circuit board, unit, often need adopt insulating resin to carry out embedding, seal to satisfy it to insulation, antidetonation, weather-proof, moistureproof and requirement such as maintain secrecy.
As the electronic unit that can effectively improve drive safety; The application on automobile of radar for backing car and tire pressure detector is universal day by day; These electronic component housings generally strengthen PA66 (polyamide 66 or nylon 66) injection moulding by spun glass; Electrical elements such as wiring board, unit are contained in inside, need to adopt insulating encapsulating material to seal, insulate and fix.According to estimates, the consumption of this resinoid of home market should be more than 200 tons/year at present.
Epoxy resin is used as Embedding Material; Can produce higher internal stress during curing; Solidify the back and when suffering the inevitably hot and cold impact of environment, also can produce higher contraction and expansion stress; These stress can influence the comparatively responsive radar for backing car of environmental stress and the safety of tire pressure detector internal electronic component, can damage these electronic devices and components fully when serious.
Organic silica gel is owing to have lower internal stress and excellent high and low temperature resistance; Become the general choice of early stage radar for backing car production, but these silica gel all belong to add-on type silica gel with glue, have cost an arm and a leg, shortcomings such as risk that catalyzer maybe poison deactivation; Especially the adhesivity extreme difference of such joint sealant and PA66; Make moisture may get into part interior, and then corrode inner components and parts, cause component failure along the gap between joint sealant and PA66 housing.Shortcoming to the add-on type organic silica gel; All the someone attempts to develop condensed type organic silicon glue both at home and abroad; But such silica gel is when improving adhesivity and curing performance; Also bring shortcomings such as discharging small molecule by-product, this small molecule by-product residues in the colloid, may influence the joint sealant bulk properties; When slowly discharging, may influence the performance of inner components and parts or peripheral devices is caused potential impact.
Radar for backing car, tire pressure detector are away from the motor car engine position; Its envrionment temperature of living in can be above 100 ℃; Owing to have moderate hardness, lower internal stress, good cold-and-heat resistent impact capacity and relative less cost, make the application of urethane resin on radar for backing car, tire pressure detector become possibility simultaneously.Yet market visible polyurethane pouring sealant product ubiquity and PA66 cementability are relatively poor or be difficult to bear the shortcomings such as harshness requirement of radar for backing car, tire pressure detector antagonism thermal shock ability.Select suitable properties-correcting agent and modification technology for use, improve the cold-and-heat resistent impact capacity of urethane resin and become successfully exploitation and be applicable to radar for backing car, tire pressure detector encapsulation key with joint sealant with the cementability of PA66.
Summary of the invention
The object of the present invention is to provide a kind of high bond strength urethane resin joint sealant and preparation method thereof.
The technical scheme that the present invention taked is:
A kind of high bond strength urethane resin joint sealant; Be made up of A component and B component, by weight, the A component contains 15～80 parts of Viscotrol C, 0～65 part of polyether glycol; The B component contains totally 15～100 parts of hydroxy-terminated polybutadienes, MDI, 0～0.05 part of promotor, 0～85 part of additive; The molar ratio of the hydroxyl of said hydroxy-terminated polybutadienes and the NCO of MDI is 0.06～0.25, and said MDI is 4, and 4'-MDI content is no less than 80 wt%; All the other are the MDI or 4 of isomery homologue, and the 4'-MDI content of isomer is no less than the modification MDI of 80 wt%.
Preferably; A kind of high bond strength urethane resin joint sealant; Form by A component and B component; By weight, the A component contains 20～50 parts of Viscotrol C, 5～30 parts of polyether glycols, and the B component contains hydroxy-terminated polybutadienes and 40～85 parts of MDI, 0.02～0.04 part of promotor, 15～60 parts of additives.
Preferably, the A component also contains 0.02～0.25 part of promotor, 5～12 parts of effect auxiliary agents, 0～75 part of additive.
Preferably, the hydroxyl value of hydroxy-terminated polybutadienes is 0.55～1.20mmol/g, and number-average molecular weight is 2000～4500.
Preferably, polyether glycol is the polyoxypropyleneglycol of molecular-weight average 1000～2000.
Preferably, the promotor in the B component is at least a in tertiary amines promotor, imidazoles promotor, organic tin promotor, the titanic acid ester; Additive in the B component is at least a in fire retardant, the softening agent.
Preferably, in the A component promotor be at least a in tertiary amines promotor, imidazoles promotor, organic tin promotor, the titanic acid ester; Effect auxiliary agent in the A component is at least a in pigment, wetting agent, flow agent, water-removal additive, anti-settling agent, the skimmer; Additive in the A component is at least a in inorganic powder, fire retardant, toughner, the softening agent.
The preparation method of above-mentioned high bond strength urethane resin joint sealant comprises the steps:
1) preparation of A component: with the raw materials mix of A component evenly after, remove bubble under the vacuum, barrelling;
2) preparation of B component: hydroxy-terminated polybutadienes, additive are joined in the reaction kettle, heat up, dewater under the vacuum, cooling adds promotor, stirs, and adds MDI, temperature reaction, cooling, barrelling.
Preferably, the preparation process of B component comprises: hydroxy-terminated polybutadienes, additive are joined in the reaction kettle, be warming up to 80～100 ℃, dewater under the vacuum; Be cooled to 55～65 ℃, add promotor, stir, add MDI; Be warming up to 80～100 ℃ of reaction 4～6 h, cooling, barrelling.
The staple of B component of the present invention be hydroxy-terminated polybutadienes with MDI synthetic prepolymer; In the preparation process of B component, additive is an inerts e, does not participate in reaction in the whole process; Mainly be in order to dilute prepolymer product; And to final prescription product generation specific performance properties, the intensification in the preparation process also vacuumizes, and purpose is to remove moisture residual in hydroxy-terminated polybutadienes and the additive.
MDI of the present invention is a diphenylmethanediisocyanate, and according to the difference of the position of NCO functional group on phenyl ring, in fact MDI has 4; 4 '-diphenylmethanediisocyanate (4; 4 '-MDI), 2,4 ' diphenylmethanediisocyanate (2,4 '-MDI), 2; 2 ' diphenylmethanediisocyanate (2,2 '-MDI) three kind of isomers.Of the present invention 4, the isomery homologue of 4 '-MDI is 2,4 '-MDI, 2,2 '-MDI.
Modification MDI of the present invention can select carbodiimide-uretonimine-modified MDI for use; Urethane-modified MDI, allophanate-modified MDI etc.; Like ten thousand magnificent MDI-100HL, MDI-100LL; Bayer DESMODUR VL, HUNTSMEN SUPRASEC 2214 etc., but the used modification MDI of the present invention need satisfy 4, and 4'-MDI content is no less than the condition of 80 wt%.
Tertiary amines promotor according to the invention comprises 1,8-diaza-dicyclo (5,4; O) undecylene-7 (that is: DBU), N; Accelerine, N, N-dimethyl-p-toluidine, N, N-Diethyl Aniline; Said imidazoles promotor comprises 2-ethyl imidazol(e), 2-ethyl-4-methylimidazole and 1-cyanoethyl-2-ethyl-4-methylimidazole, and said organic tin promotor comprises stannous oleate, stannous octoate or dibutyltin dilaurate.
The middle promotor of A component of the present invention is in order to promote A component and B component to solidify, and the promotor in the B component is in order to promote hydroxy-terminated polybutadienes and the MDI synthetic prepolymer in the B component.
The method of calculation of the NCO molar ratio of the hydroxyl of hydroxy-terminated polybutadienes of the present invention and MDI are: the mol ratio of OH/NCO=(quality of hydroxyl value * hydroxy-terminated polybutadienes): [(quality of the mass percent * MDI of the NCO of MDI)/(42g/mol)]; Wherein, 42 g/mol are the molar mass of NCO.
Urethane resin joint sealant method of use of the present invention: A component and the B component mass ratio by 1:0.2～1 is mixed; Be used for electronics or electric component embedding, seal, under the room temperature, but 4～6 h gels; About 8 h can apparently solidify, and reach maximum strength (30A～80A) behind 48 h.
The invention has the beneficial effects as follows:
Urethane resin joint sealant of the present invention has high bond strength; Especially the adhesiveproperties with plastic materials (PA66) such as nylon is good; Also have good electric property, lower internal stress and excellent thermal shock resistance, particularly be applicable to radar for backing car, tire pressure monitor etc. to internal stress require comparatively harsh electronic unit embedding, seal.
Description of drawings
Fig. 1 is that the joint sealant of embodiment 1 has the bonding lab diagram;
Fig. 2 is that the joint sealant of embodiment 2 has the bonding lab diagram;
Fig. 3 is that the joint sealant of embodiment 3 has the bonding lab diagram;
Fig. 4 is that the joint sealant of embodiment 4 has the bonding lab diagram;
Fig. 5 is that the joint sealant of Comparative Examples 1 has the bonding lab diagram;
Fig. 6 is that the joint sealant of Comparative Examples 2 has the bonding lab diagram;
Fig. 7 is that the joint sealant of Comparative Examples 3 has the bonding lab diagram;
Fig. 8 is that the joint sealant of Comparative Examples 4 has the bonding lab diagram.
Embodiment
Embodiment below in conjunction with concrete is further described the present invention, but does not limit to so.
The effect auxiliary agent that the A component adopts among the embodiment: the wetting agent marque is BYK-W980; The flow agent marque is BYK370; The water-removal additive marque is Siliporite SA1720, and the anti-settling agent marque is HDK T40, and the skimmer marque is BYK-A 535;
The additive that the A component adopts among the embodiment: inorganic powder is an aluminium-hydroxide powder, and softening agent is a triphenylphosphate;
The additive that the B component adopts among the embodiment: fire retardant is IPPP (a cumyl phenyl phosphate ester), and softening agent is TPP (triphenyl phosphite);
Per-cent in embodiment and the Comparative Examples is mass percent.
Embodiment 1
A kind of high bond strength urethane resin joint sealant is made up of A component and B component, by weight,
A component: 31 parts of Viscotrol C (hydroxyl equivalent is 345, and the average hydroxy functionality is 2.7), 12 parts of polyoxypropyleneglycols (molecular-weight average is 1000), 0.2 part of promotor (DBU), 48 parts of inorganic powders, 8.2 parts of effect auxiliary agents;
B component: 26.7 parts of hydroxy-terminated polybutadieness (hydroxyl value is 0.9mmol/g, and number-average molecular weight is 2300), 33.3 parts of MDI (MDI-100HL, 4,4'-MDI content >=90%, NCO content 29%), 0.03 part of promotor (DABCO 33LV), 40 parts of fire retardants;
8.2 parts of above-mentioned effect auxiliary agents are made up of for 6.5 parts 0.35 part of black pigment, 0.5 part of skimmer, 0.6 part of wetting agent, 0.25 part of anti-settling agent, water-removal additive.
Above-mentioned high bond strength urethane resin joint sealant preparation method:
1) preparation of A component: the raw material of A component is added Scattered Kettle, be uniformly dispersed, remove bubble under the vacuum, barrelling;
2) preparation of B component: hydroxy-terminated polybutadienes, fire retardant are joined in the reaction kettle, be warming up to 80 ℃, dewater under the vacuum, be cooled to 60 ℃, add promotor, stir, add MDI, be warming up to 80 ℃ of reaction 5 h, cooling, barrelling.
Embodiment 2
A kind of high bond strength urethane resin joint sealant is made up of A component and B component, by weight,
A component: 20.5 parts of Viscotrol C (hydroxyl equivalent is 345, and the average hydroxy functionality is 2.7), 7.9 parts of polyoxypropyleneglycols (molecular-weight average is 1000), 0.2 part of promotor (DBU), 62.6 parts of inorganic powders, 8.2 parts of effect auxiliary agents;
B component: 26.7 parts of hydroxy-terminated polybutadieness (hydroxyl value is 0.9mmol/g, and number-average molecular weight is 2300), 33.3 parts of MDI (MDI-100HL, 4,4'-MDI content >=90%, NCO content 29%), 0.03 part of promotor (DABCO 33LV), 40 parts of fire retardants;
8.2 parts of above-mentioned effect auxiliary agents are made up of for 6.5 parts 0.35 part of black pigment, 0.5 part of skimmer, 0.6 part of wetting agent, 0.25 part of anti-settling agent, water-removal additive.
Above-mentioned high bond strength urethane resin joint sealant preparation method:
1) preparation of A component: the raw material of A component is added Scattered Kettle, be uniformly dispersed, remove bubble under the vacuum, barrelling;
2) preparation of B component: hydroxy-terminated polybutadienes, fire retardant are joined in the reaction kettle, be warming up to 100 ℃, dewater under the vacuum, be cooled to 55 ℃, add promotor, stir, add MDI, be warming up to 100 ℃ of reaction 4 h, cooling, barrelling.
Embodiment 3
A kind of high bond strength urethane resin joint sealant is made up of A component and B component, by weight,
A component: 31 parts of Viscotrol C (hydroxyl equivalent is 345, and the average hydroxy functionality is 2.7), 12 parts of polyoxypropyleneglycols (molecular-weight average is 1000), 0.2 part of promotor (DBU), 48 parts of inorganic powders, 8.2 parts of effect auxiliary agents;
B component: 20.5 parts of hydroxy-terminated polybutadieness (hydroxyl value is 0.9mmol/g, and number-average molecular weight is 2300), 25.5 parts of MDI (MDI-100HL, 4,4'-MDI content >=90%, NCO content 29%), 0.03 part of promotor (DABCO 33LV), 54 parts of fire retardants;
8.2 parts of above-mentioned effect auxiliary agents are by 0.35 part of black pigment, 0.5 part of skimmer, 0.6 part of wetting agent, 0.25 part of anti-settling agent, 6.5 parts of compositions of water-removal additive.
Above-mentioned high bond strength urethane resin joint sealant preparation method:
1) preparation of A component: the raw material of A component is added Scattered Kettle, be uniformly dispersed, remove bubble under the vacuum, barrelling;
2) preparation of B component: hydroxy-terminated polybutadienes, fire retardant are joined in the reaction kettle, be warming up to 90 ℃, dewater under the vacuum, be cooled to 65 ℃, add promotor, stir, add MDI, be warming up to 90 ℃ of reaction 6 h, cooling, barrelling.
Embodiment 4
A kind of high bond strength urethane resin joint sealant is made up of A component and B component, by weight,
A component: 80 parts of Viscotrol C (hydroxyl equivalent is 345, and the average hydroxy functionality is 2.7), 65 parts of polyoxypropyleneglycols (molecular-weight average is 2000);
The B component: the OH/NCO molar ratio is that (hydroxyl value is 0.55mmol/g for 0.25 hydroxy-terminated polybutadienes; Number-average molecular weight is 4500), MDI (4,4'-MDI content 80 %, 2; 4'-MDI content 20%; NCO content 33.5%) totally 15 parts, 0.05 part of promotor (dibutyl tin laurate), 85 parts in softening agent.
Above-mentioned high bond strength urethane resin joint sealant preparation method:
1) preparation of A component: the raw material of A component is added Scattered Kettle, be uniformly dispersed, remove bubble under the vacuum, barrelling;
2) preparation of B component: hydroxy-terminated polybutadienes, softening agent are joined in the reaction kettle, be warming up to 80 ℃, dewater under the vacuum, be cooled to 55 ℃, add promotor, stir, add MDI, be warming up to 80 ℃ of reaction 4 h, cooling, barrelling.
Embodiment 5
A kind of high bond strength urethane resin joint sealant is made up of A component and B component, by weight,
A component: 15 parts of Viscotrol C (hydroxyl equivalent is 345, and the average hydroxy functionality is 2.7);
The B component: the OH/NCO molar ratio is totally 100 parts of 0.15 hydroxy-terminated polybutadieness (hydroxyl value is 0.9mmol/g, and number-average molecular weight is 2300), MDI (pure MDI, 4,4'-MDI content is more than 99%, NCO content 33.5%).
Above-mentioned high bond strength urethane resin joint sealant preparation method:
1) preparation of A component: the raw material of A component is added Scattered Kettle, be uniformly dispersed, remove bubble under the vacuum, barrelling;
2) preparation of B component: hydroxy-terminated polybutadienes is joined in the reaction kettle, be warming up to 100 ℃, dewater under the vacuum, be cooled to 60 ℃, add MDI, be warming up to 100 ℃ of reaction 5 h, cooling, barrelling.
Embodiment 6
A kind of high bond strength urethane resin joint sealant is made up of A component and B component, by weight,
A component: 40 parts of Viscotrol C (hydroxyl equivalent is 300, and the average hydroxy functionality is 2.4), 35 parts of polyoxypropyleneglycols (molecular-weight average is 1000);
The B component: the OH/NCO molar ratio is that (hydroxyl value is 1.0mmol/g for 0.06 hydroxy-terminated polybutadienes; Number-average molecular weight is 2200), (mass ratio that MDI-100HL, MDI-50 press 4:1 mixes MDI; 4,4'-MDI content is more than 82%, NCO content 30.5%) totally 65 parts; 0.02 part of promotor (DABCO 33LV), 35 parts of fire retardants.
Above-mentioned high bond strength urethane resin joint sealant preparation method:
1) preparation of A component: the raw material of A component is added Scattered Kettle, be uniformly dispersed, remove bubble under the vacuum, barrelling;
2) preparation of B component: hydroxy-terminated polybutadienes, fire retardant are joined in the reaction kettle, be warming up to 90 ℃, dewater under the vacuum, be cooled to 65 ℃, add promotor, stir, add MDI, be warming up to 90 ℃ of reaction 6 h, cooling, barrelling.
Embodiment 7
A kind of high bond strength urethane resin joint sealant is made up of A component and B component, by weight,
A component: 15 parts of Viscotrol C (hydroxyl equivalent is 345, and the average hydroxy functionality is 2.7), 0.02 part of promotor (stannous octoate), 5 parts of effect auxiliary agents;
The B component: the OH/NCO molar ratio is 100 parts of 0.06 hydroxy-terminated polybutadienes (hydroxyl value is 0.55mmol/g, and number-average molecular weight is 4500), MDI (4,4'-MDI content 85 %, 4, the isomery homologue content 15% of 4'-MDI, NCO content 33.5%);
Above-mentioned effect auxiliary agent is a water-removal additive.
Above-mentioned high bond strength urethane resin joint sealant preparation method:
1) preparation of A component: the raw material of A component is added Scattered Kettle, be uniformly dispersed, remove bubble under the vacuum, barrelling;
2) preparation of B component: hydroxy-terminated polybutadienes is joined in the reaction kettle, be warming up to 100 ℃, dewater under the vacuum, be cooled to 55 ℃, add MDI, be warming up to 100 ℃ of reaction 5 h, cooling, barrelling.
Embodiment 8
A kind of high bond strength urethane resin joint sealant is made up of A component and B component, by weight,
A component: 80 parts of Viscotrol C (hydroxyl equivalent is 300, and the average hydroxy functionality is 2.4), 65 parts of polyoxypropyleneglycols (molecular-weight average is 2000), 0.25 part of promotor (DBU), 12 parts of effect auxiliary agents, 75 parts of inorganic powders;
The B component: the OH/NCO molar ratio is 0.25 hydroxy-terminated polybutadienes (hydroxyl value is 1.0mmol/g, and number-average molecular weight is 2200), MDI (MDI-100 HL, 4; 4'-MDI content >=90%; Totally 15 parts of NCO content 29%, 0.05 part of promotor (dibutyl tin laurate), 85 parts of fire retardants;
12 parts of above-mentioned effect auxiliary agents are by 0.15 part of black pigment, 2 parts of flow agents, 0.5 part of skimmer, 0.6 part of wetting agent, 0.25 part of anti-settling agent, 8.5 parts of compositions of water-removal additive.
Above-mentioned high bond strength urethane resin joint sealant preparation method:
1) preparation of A component: the raw material of A component is added Scattered Kettle, be uniformly dispersed, remove bubble under the vacuum, barrelling;
2) preparation of B component: hydroxy-terminated polybutadienes, fire retardant are joined in the reaction kettle, be warming up to 100 ℃, dewater under the vacuum, be cooled to 55 ℃, add promotor, stir, add MDI, be warming up to 100 ℃ of reaction 5 h, cooling, barrelling.
Embodiment 9
A kind of high bond strength urethane resin joint sealant is made up of A component and B component, by weight,
A component: 50 parts of Viscotrol C (hydroxyl equivalent is 300, and the average hydroxy functionality is 2.4), 30 parts of polyoxypropyleneglycols (molecular-weight average is 2000);
The B component: the OH/NCO molar ratio is that (hydroxyl value is 0.55mmol/g for 0.25 hydroxy-terminated polybutadienes; Number-average molecular weight is 4500), MDI (4,4'-MDI content 80 %, 2; 4'-MDI content 20%; NCO content 30.5%) totally 85 parts, 0.04 part of promotor (dibutyl tin laurate), 15 parts in softening agent.
Above-mentioned high bond strength urethane resin joint sealant preparation method:
1) preparation of A component: the raw material of A component is added Scattered Kettle, be uniformly dispersed, remove bubble under the vacuum, barrelling;
2) preparation of B component: hydroxy-terminated polybutadienes, softening agent are joined in the reaction kettle, be warming up to 80 ℃, dewater under the vacuum, be cooled to 55 ℃, add promotor, stir, add MDI, be warming up to 80 ℃ of reaction 4 h, cooling, barrelling.
Embodiment 10
A kind of high bond strength urethane resin joint sealant is made up of A component and B component, by weight,
A component: 20 parts of Viscotrol C (hydroxyl equivalent is 345, and the average hydroxy functionality is 2.7), 5 parts of polyoxypropyleneglycols (molecular-weight average is 1500);
The B component: the OH/NCO molar ratio is that (hydroxyl value is 1.2mmol/g for 0.06 hydroxy-terminated polybutadienes; Number-average molecular weight is 2000), MDI (4,4'-MDI content 85 %, 4; The isomery homologue content 15% of 4'-MDI; NCO content 33.5%) totally 40 parts, 0.02 part of promotor (DABCO 33LV), 60 parts of fire retardants.
Above-mentioned high bond strength urethane resin joint sealant preparation method:
1) preparation of A component: the raw material of A component is added Scattered Kettle, be uniformly dispersed, remove bubble under the vacuum, barrelling;
2) preparation of B component: hydroxy-terminated polybutadienes, fire retardant are joined in the reaction kettle, be warming up to 100 ℃, dewater under the vacuum, be cooled to 55 ℃, add promotor, stir, add MDI, be warming up to 100 ℃ of reaction 5 h, cooling, barrelling.
Embodiment 11
A kind of high bond strength urethane resin joint sealant is made up of A component and B component, by weight,
A component: 50 parts of Viscotrol C (hydroxyl equivalent is 300, and the average hydroxy functionality is 2.4), 30 parts of polyoxypropyleneglycols (molecular-weight average is 2000), 0.02 part of promotor (DBU), 12 parts of effect auxiliary agents;
The B component: the OH/NCO molar ratio is that (hydroxyl value is 1.2mmol/g for 0.25 hydroxy-terminated polybutadienes; Number-average molecular weight is 2000), MDI (4,4'-MDI content 80 %, 2; 4'-MDI content 20%; NCO content 33.5%) totally 85 parts, 0.04 part of promotor (dibutyl tin laurate), 15 parts in softening agent;
12 parts of above-mentioned effect auxiliary agents are by 0.15 part of black pigment, 2 parts of flow agents, 0.5 part of skimmer, 0.6 part of wetting agent, 0.25 part of anti-settling agent, 8.5 parts of compositions of water-removal additive.
Above-mentioned high bond strength urethane resin joint sealant preparation method:
1) preparation of A component: the raw material of A component is added Scattered Kettle, be uniformly dispersed, remove bubble under the vacuum, barrelling;
2) preparation of B component: hydroxy-terminated polybutadienes, softening agent are joined in the reaction kettle, be warming up to 80 ℃, dewater under the vacuum, be cooled to 55 ℃, add promotor, stir, add MDI, be warming up to 80 ℃ of reaction 4 h, cooling, barrelling.
Embodiment 12
A kind of high bond strength urethane resin joint sealant is made up of A component and B component, by weight,
A component: 20 parts of Viscotrol C (hydroxyl equivalent is 345, and the average hydroxy functionality is 2.7), 5 parts of polyoxypropyleneglycols (molecular-weight average is 1600), 0.25 part of promotor (DBU), 5 parts of effect auxiliary agents, 35 parts of inorganic powders, 40 parts in softening agent;
The B component: the OH/NCO molar ratio is 0.06 hydroxy-terminated polybutadienes (hydroxyl value is 0.55mmol/g, and number-average molecular weight is 4500), MDI (pure MDI, 4; 4'-MDI content >=90%; NCO content 33.5%) totally 40 parts, 0.02 part of promotor (DABCO 33LV), 60 parts of fire retardants;
5 parts of above-mentioned effect auxiliary agents are by 0.5 part of skimmer, 0.6 part of wetting agent, 0.4 part of anti-settling agent, 3.5 parts of compositions of water-removal additive.
Above-mentioned high bond strength urethane resin joint sealant preparation method:
1) preparation of A component: the raw material of A component is added Scattered Kettle, be uniformly dispersed, remove bubble under the vacuum, barrelling;
2) preparation of B component: hydroxy-terminated polybutadienes, fire retardant are joined in the reaction kettle, be warming up to 100 ℃, dewater under the vacuum, be cooled to 55 ℃, add promotor, stir, add MDI, be warming up to 100 ℃ of reaction 5 h, cooling, barrelling.
Comparative Examples 1
A kind of urethane resin joint sealant is made up of A component and B component, by weight,
The A component: (hydroxyl equivalent is 345 to Viscotrol C; The average hydroxy functionality is 2.7) 31 parts; 26.7 parts of hydroxy-terminated polybutadieness (hydroxyl value is 0.9mmol/g, and number-average molecular weight is 2300), 0.2 part of promotor (DBU); 48 parts of inorganic powders, 0.35 part of black pigment, 0.5 part of skimmer, 0.6 part of wetting agent, 0.25 part of anti-settling agent, 6.5 parts of water-removal additives;
B component: 12 parts of polyoxypropyleneglycols (molecular-weight average is 1000), MDI (MDI-100HL, 4,4'-MDI content >=90wt%) 33.3 parts, 0.03 part of promotor (DABCO 33LV), 40 parts of fire retardants.
The preparation method is with embodiment 1, only the location swap that adds of the hydroxy-terminated polybutadienes among embodiment 1 preparation method, polyoxypropyleneglycol.
Comparative Examples 2
A kind of high bond strength urethane resin joint sealant is made up of A component and B component, by weight,
The A component: (hydroxyl equivalent is 345 to Viscotrol C; The average hydroxy functionality is 2.7) 31 parts, 12 parts of polyoxypropyleneglycols (molecular-weight average is 1000), (hydroxyl value is 0.9mmol/g to hydroxy-terminated polybutadienes; Number-average molecular weight is 2300) 26.7 parts, 0.2 part of promotor (DBU), 48 parts of inorganic powders, 0.35 part of black pigment, 0.5 part of skimmer, 0.6 part of wetting agent, 0.25 part of anti-settling agent, 6.5 parts of water-removal additives;
B component: MDI (MDI-100HL, 4,4'-MDI content >=90wt%) 33.3 parts, 0.03 part of promotor (DABCO 33LV), 40 parts of fire retardants.
Above-mentioned high bond strength urethane resin joint sealant preparation method:
1) preparation of A component: the raw material of A component is added Scattered Kettle, be uniformly dispersed, remove bubble under the vacuum, barrelling;
2) preparation of B component: hydroxy-terminated polybutadienes, fire retardant are joined in the reaction kettle, be warming up to 80 ℃, dewater under the vacuum, be cooled to 60 ℃, add promotor, stir, add MDI, be warming up to 80 ℃ of reaction 5 h, cooling, barrelling.
Comparative Examples 3
A kind of urethane resin joint sealant is made up of A component and B component, and constitutive material is identical with embodiment 4 with each raw materials quality part; Only with the MDI 4 of B component among the embodiment 4,4'-MDI content 80 %, 2; 4'-MDI content 20%) replace with MDI (4; 4'-MDI content 70 %, 2,4'-MDI content 30%).
Comparative Examples 4
A kind of urethane resin joint sealant is made up of A component and B component, and constitutive material is identical with embodiment 4 with each raw materials quality part; Only with the MDI (4 of B component among the embodiment 4; 4'-MDI content 80 %, 2,4'-MDI content 20%) (mass ratio that MDI-100HL, MDI-50 press 1:4 mixes to replace with MDI; 4,4'-MDI content 58～60%).
The high bond strength urethane resin joint sealant of embodiment 1～3 is carried out the detection of each item physical index, and detected result is seen table 1.The condition of the used nylon plastic material PA66 of test experience is all identical; Can know by table 1; The adhesive property of urethane resin joint sealant of the present invention and nylon plastic material PA66 is good; Can make the cohesive failure of the urethane resin joint sealant after the curing, so urethane resin joint sealant of the present invention has high bond strength.
The main physical index of the urethane resin joint sealant of each embodiment of table 1
| ? | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Hardness (Shore A) | 55 | 70 | 40 |
| Heat-conduction coefficient (Wm -1K -1) | 0.35 | 0.70 | 0.42 |
| Insulation strength (KV/mm) | 18 | 19 | 17 |
| The self-extinguishing ability (UL94,6mm) | V-1 | V-0 | V-0 |
| -40 ℃～80 ℃, 1000 cold shock testings | There are not cracking, shrinking away from theshell | There are not cracking, shrinking away from theshell | There are not cracking, shrinking away from theshell |
| Viscosifying power with PA66 | The joint sealant cohesive failure | The joint sealant cohesive failure | The joint sealant cohesive failure |
Embodiment 1～3 and the adhesion test result that PA66 carries out see Fig. 1～3; Can know by Fig. 1～3; The joint sealant body of abutting edge all is destroyed, and this explanation bonding force is greater than the intensity that can bear of joint sealant itself, and adhesivity has reached the perfect condition of such test.
The adhesion test that respectively joint sealant and the PA66 of embodiment 4 and Comparative Examples 1～4 is carried out similarity condition.The test-results of Comparative Examples 1 is seen Fig. 5; The test-results of Comparative Examples 2 is seen Fig. 6; Comparative Examples 1 is with respect to embodiment 1, and MDI and polyoxypropyleneglycol reaction synthetic prepolymer are as the B component, but not MDI and hydroxy-terminated polybutadienes reaction; Fig. 5 and Fig. 1 contrast can be known the joint sealant no adhesion ability that Comparative Examples 1 obtains.Comparative Examples 2 is with respect to embodiment 1, and hydroxy-terminated polybutadienes and MDI branch are opened and made an addition to A component, B component, and Fig. 6 and Fig. 1 contrast can be known the joint sealant no adhesion ability that Comparative Examples 2 obtains.Interpretation by Comparative Examples 1～2 can get: if not with MDI (4; 4'-MDI content is no less than 80 %) be prepared into prepolymer as B component (solidifying agent) with hydroxy-terminated polybutadienes; And directly with 4,4'-MDI content is no less than the MDI of 80 % as B component (solidifying agent), and the joint sealant of gained and PA66 almost do not have any cementability; Therefore, this bright prepolymer with MDI and hydroxy-terminated polybutadienes formation is most important as the B component.
The test-results of embodiment 4 is seen Fig. 4, and the test-results of Comparative Examples 3 is seen Fig. 7, and the test-results of Comparative Examples 4 is seen Fig. 8; Fig. 4 shows joint sealant cohesive failure and interfacial failure, so the joint sealant of embodiment 4 has high bond strength, Fig. 7 and 8 shows only slick interfacial failure; Basically do not have cementability, contrast can be known, the basic no adhesion of the joint sealant that Comparative Examples 3～4 obtains; It is thus clear that 4 among the MDI, 4'-MDI content are less than the joint sealant no adhesion ability that 80 % make; Among the MDI of the present invention 4,4'-MDI content is big to the adhesive property influence.
Claims (9)
1. a high bond strength urethane resin joint sealant is made up of A component and B component, by weight,
The A component contains 15～80 parts of Viscotrol C, 0～65 part of polyether glycol,
The B component contains totally 15～100 parts of hydroxy-terminated polybutadienes, MDI, 0～0.05 part of promotor, 0～85 part of additive,
The molar ratio of the hydroxyl of said hydroxy-terminated polybutadienes and the NCO of MDI is 0.06～0.25,
Said MDI is 4, and 4'-MDI content is no less than 80 wt%, and all the other are the MDI or 4 of isomery homologue, and the 4'-MDI content of isomer is no less than the modification MDI of 80 wt%.
2. high bond strength urethane resin joint sealant according to claim 1 is characterized in that: the A component contains 20～50 parts of Viscotrol C, 5～30 parts of polyether glycols,
The B component contains hydroxy-terminated polybutadienes and 40～85 parts of MDI, 0.02～0.04 part of promotor, 15～60 parts of additives.
3. high bond strength urethane resin joint sealant according to claim 1 and 2 is characterized in that: the A component also contains 0.02～0.25 part of promotor, 5～12 parts of effect auxiliary agents, 0～75 part of additive.
4. high bond strength urethane resin joint sealant according to claim 1 and 2 is characterized in that: the hydroxyl value of hydroxy-terminated polybutadienes is 0.55～1.20mmol/g, and number-average molecular weight is 2000～4500.
5. high bond strength urethane resin joint sealant according to claim 1 and 2 is characterized in that: polyether glycol is the polyoxypropyleneglycol of molecular-weight average 1000～2000.
6. high bond strength urethane resin joint sealant according to claim 1 and 2 is characterized in that: the promotor in the B component is at least a in tertiary amines promotor, imidazoles promotor, organic tin promotor, the titanic acid ester; Additive in the B component is at least a in fire retardant, the softening agent.
7. high bond strength urethane resin joint sealant according to claim 3 is characterized in that: in the A component promotor be at least a in tertiary amines promotor, imidazoles promotor, organic tin promotor, the titanic acid ester; Effect auxiliary agent in the A component is at least a in pigment, wetting agent, flow agent, water-removal additive, anti-settling agent, the skimmer; Additive in the A component is at least a in inorganic powder, fire retardant, toughner, the softening agent.
8. the preparation method of claim 1 or 2 each described high bond strength urethane resin joint sealants comprises the steps:
The preparation of A component: with the raw materials mix of A component evenly after, remove bubble under the vacuum, barrelling;
The preparation of B component: hydroxy-terminated polybutadienes, additive are joined in the reaction kettle, heat up, dewater under the vacuum, cooling adds promotor, stirs, and adds MDI, temperature reaction, cooling, barrelling.
9. the preparation method of high bond strength urethane resin joint sealant according to claim 8 is characterized in that: the preparation process of B component comprises: hydroxy-terminated polybutadienes, additive are joined in the reaction kettle, be warming up to 80～100 ℃; Dewater under the vacuum, be cooled to 55～65 ℃, add promotor; Stir, add MDI, be warming up to 80～100 ℃ of reaction 4～6 h; Cooling, barrelling.
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