CN102618019B - Polyurethane reaction ball and preparing method thereof - Google Patents
Polyurethane reaction ball and preparing method thereof Download PDFInfo
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Abstract
The invention discloses a polyurethane reaction ball which is a microcellular polyurethane elastomer prepared through raw materials including polymer component A and prepolymer component B. The invention further discloses a method for preparing the reaction ball, which includes: mixing and stirring polyether polyols, foaming agents, chain extenders, color paste and catalysts to obtain the polymer component A; and evenly mixing and stirring the polymer component A and the prepolymer component B according to a certain proportion at temperature of 5-32 DEG C, and pouring the mixture into a reaction ball mold for aging to obtain the polyurethane reaction ball. The foam density of the reaction ball is 100-600kg/m<3>, hardness of the reaction ball is Shore A40+/-10, free-falling resilience can reach 80-90%, and property requirements of high-level reaction balls are met. In addition, the polyurethane reaction ball and the preparing method thereof have good technology processing characteristics, spalling during contraction and mold opening is avoided, and product defective percentage is reduced.
Description
Technical field
The present invention relates to a kind of reaction sphere and preparation method thereof, particularly a kind of microporous polyurethane elastomer hexagonal reaction sphere and preparation method thereof.
Background technology
Sexangular ball also claims reaction sphere, by solid rubber, is made, and throwing can nondirectionally rebound on the ground, and the rebound performance that freely lands determines to land the speed of bounce-back, and the rebound performance that freely lands is better, and the speed of bounce-back of landing is just faster.Therefore freely land the key index of resilience as evaluation response ball quality.Reaction sphere is the essential product of exercise speed of response in the world, is applicable to tennis, shuttlecock, the sportsmen such as table tennis.
Traditional hexagonal reaction sphere is to be made by rubber, and it has good low temperature kindliness, higher elasticity, and throwing on the ground nondirectional bounce-back speed is very fast, and sportsmen can practise speed of response well.But there is following problem in rubber item: the resistance to ozone of goods, loss of properties on aging, the rubber that contains unsaturated double-bond is in processing, storage, transportation, owing to being heated, the comprehensive action of the extraneous factor such as light, oxygen, material internal generation physics or chemical transformation, make flexibility decrease so that can not use.
Urethane full name is polyurethane(s), is the general designation that contains the macromolecular cpd of repetition carbamate groups on main chain.It is to be formed by organic diisocyanate or polyisocyanates and dihydroxyl or polyol addition polymerization.The resistance to ozone of urethane, ageing-resistant ability are strong, and the prolongation that performance can be not in time and obviously declining has extended the work-ing life of reaction sphere greatly.Microporous polyurethane elastic foam, owing to having excellent wear resistance, ageing-resistant performance, fabulous rebound resilience, has been widely used in the materials such as sole, steering wheel for vehicle, furniture armrest.
Conventional urethane microcellular elastomeric foam, the resilience of freely landing is generally 30-50%, even if adopt expensive polytetramethylene polyether glycol as main raw material, goods freely land resilience also with regard to 70% left and right, more conventional elastomeric material is much lower, cannot be applied to high-level reaction sphere.
The Chinese patent that publication number is CN 101134843A provides a kind of highly-elastic urethane elastomer composition, and adopting polytetramethylene polyether glycol is main raw material, and goods have excellent mechanical property and impact resilience, and the resilience of freely landing reaches 70%.It is mainly used in the making of high-elastic wheel for roller skates or slide plate wheel.
The Chinese patent that publication number is CN1126770C provides a kind of moulded polyyurethane material method.Its performed polymer NCO content is 3-15wt%, the 0.8-5wt/% that in formula, the water yield is whole components, and rebound resilience is 55-80%.
Still the formula and the preparation technology that there is no at present bibliographical information polyurethane reaction ball, therefore still lack a kind of microporous polyurethane elastic foam with higher rebound performance and low viscosity raw material, can be used in the production of toy ball and high-level hexagonal reaction sphere.
The microporous polyurethane elastomer that the present invention adopts higher modification MDI (NCO% > 15wt/%, viscosity < 500mPas) to prepare, resilience can reach 80%-90%, and the use of low viscosity raw material has guaranteed the mobility that goods are good, can effectively avoid the defects such as pin hole.
Summary of the invention
One of object of the present invention is to provide a kind of polyurethane reaction ball, and foam resilience and rubber item are suitable, and the resilience of freely landing is greater than 80%, and has traditional elastomeric material incomparable work-ing life.
Another object of the present invention is to provide a kind of preparation method of polyurethane reaction ball, the method technique is simple, and combination material room temperature can stably stored, without crystallization, can operate in room temperature.And material viscosity is low, goods good fluidity, can effectively avoid the defects such as pin hole.
A polyurethane reaction ball, described reaction sphere is the microcellular polyurethane elastomer being prepared from interior raw material by comprising polymeric constituent A and pre-polymer component B, it is characterized in that: described reaction sphere foam density 100-600kg/m
3, preferred 180-580kg/m
3; Hardness ShoreA 40 ± 10, preferably ShoreA 40 ± 5; The resilience of freely landing can reach 80%-90%, preferably 81-87.
Described polymeric components A comprises:
A1,90-99.9 mass parts, preferably 92-99.2 mass parts polyether glycol;
A2,0.1-10 mass parts, preferably the frothing aid of 0.8-8, comprises whipping agent, catalyzer, chainextender, mill base;
Described polyether glycol a1 number-average molecular weight 2000-8000, preferred 3000-6000, more preferably 3500-6000; Oxygen ethylidene content is 30-99wt%, preferred 50-99wt%, more preferably 60-99wt%; Average functionality is 2-6, preferably 2.1-4, more preferably 2.3-3.5.Described polyether glycol a1 is made by this area any conventional method by ethylene oxide polymer or oxyethane and epoxypropane polymer make by this area any conventional method.The preferred propylene glycol of initiator, glycerine, TriMethylolPropane(TMP), tetramethylolmethane.
Described prepolymer component B comprises:
20-50 mass parts, the modification MDI of preferred 20-45 mass parts, NCO content is 15.1-30wt%, preferably 16-25wt%, more preferably 17-23wt%;
Described modification MDI is the ester modified isocyanic ester of ammonia of the NCO end-blocking that obtained by polyvalent alcohol and isocyanate reaction and the mixture of isocyanic ester; Described isocyanic ester is the mixture of diphenylmethanediisocyanate and poly methylene poly phenyl poly isocyanate arbitrary proportion; It is 2000-10000 that described polyvalent alcohol is selected from number-average molecular weight, preferably 2000-9000, more preferably 3000-9000; Average functionality 2-3, preferably the polyether glycol b1 of 2.2-2.8.
Described polyether glycol b1 is comprised of following polyethers: the polyether glycol b1 total amount of (a) take is benchmark, 0-96wt%, the number-average molecular weight 2000-6000 of preferred 1-90wt%, the polyether glycol b11 that preferably 2500-5500 and average functionality are 2-3; (b) 4-100wt%, preferred 10-99wt% number-average molecular weight 6000-10000, the polyether glycol b12 that preferably 7000-9900 and average functionality are 2-3.
Polyether glycol b11 and polyether glycol b12 are made by this area any conventional method by ethylene oxide polymer or are made by this area any conventional method by oxyethane and epoxypropane polymer.
In the present invention, described polyether glycol, molecular weight 2000-8000, oxygen ethylidene content is 30-99wt%, functionality is 2-6.
Frothing aid includes but not limited to whipping agent, chainextender, mill base, catalyzer.Wherein whipping agent is essential component, and other can be selected as required.
Described whipping agent can be water, N
2, CO
2, one or more of chloro fluorocarbon compound, Hydrochlorofluorocarbons compound.
Preferably, described whipping agent is water, and to take the total amount of polymeric constituent A be benchmark, and the content of water is 0.1-0.6wt%, preferably 0.15-0.5wt%; It is one or more in 200 polyoxyethylene glycol that described chainextender is selected from glycol ether, dipropylene glycol, ethylene glycol, propylene glycol, BDO and number-average molecular weight.
Described mill base is selected from but is not limited to one or more in redness, orange, yellow, green, blue, purple and black color paste.
Described catalyzer is selected from but is not limited to amines catalyst, preferably two (dimethylaminoethyl) ether, triethylenediamine, N, one or more of N-dimethylcyclohexylamine, five methyl diethylentriamine.
Polyurethane reaction ball of the present invention can adopt normal pouring method to produce, but the present invention is preferably as follows method, is prepared:
1) by polyether glycol a1, whipping agent, chainextender, mill base, catalyst mix, then with high speed shear agitator, stir 8-15 minute, stirring velocity 1000-3000 rev/min, obtains polymeric components A;
2) step 1 resulting polymers component A and modification MDI are being uniformly mixed, are pouring reaction sphere mould into, slaking, obtains polyurethane reaction ball.
Reaction sphere in the present invention is two component reaction type polyurethane materials, and the polyether glycol a1, whipping agent, chainextender, mill base, the catalyzer that are labeled as polymeric components A are pre-mixed thing, and are labeled as the modification MDI of prepolymer component B.
Preferably, during 25 ℃ of described polymeric components A viscosity, be 200-1500mPas, preferred 300-1200mPas; During 25 ℃ of prepolymer component B viscosity, be 50-499mPas, preferred 80-450mPas.
The temperature that described polyether glycol a1, whipping agent, chainextender, mill base and catalyzer are pre-mixed is 5-35 ℃, and best 15-25 ℃ obtains polymeric components A in advance after mixing; Then by polymeric components A and modification MDI (prepolymer component B), temperature when wherein A, B component mix is 15-32 ℃, best 22-28 ℃.
A, with after B component mixing 5-10s, is poured into 30-60 ℃ by metered proportions, and preferably, in the reaction sphere mould mould of 34-52 ℃, the curing time is 5-10min, preferred 6-8min, and die sinking obtains microporous polyurethane foam.
Wherein, in described modification MDI, the ratio of [OH] in the mixture of [NCO] and described polyether glycol a1 and whipping agent is 1.1-1.4: 1; Preferred 1.15-1.38: 1.
In the present invention, described " poly methylene poly phenyl poly isocyanate " is all greater than the mixture of 2 polyisocyanates for average phenyl ring number and average isocyanate group number.
Oxygen ethylidene content is in polyethers building-up process, and oxyethane charging capacity accounts for the mass percent of polyethers.
As everyone knows, goods elasticity is relevant with the degree that is separated and the soft section of phase second-order transition temperature of urethane itself.The degree that is separated is higher, and goods elasticity is better, and vice versa; Soft section of phase second-order transition temperature is lower, and the molecular chain movement Shaoxing opera that is elastomeric state in room temperature is strong, and elasticity is better.NCO group reacts with water and generates urea, the hard section of the rich urea of differing molecular is gathered into urea phase hard area because of hydrogen bond action, because the thermodynamics uncompatibility of soft or hard section produces microphase-separated, but microphase-separated is generally incomplete, have a small amount of hard section be dispersed in soft section mutually in, when causing being separated degree variation, also make the second-order transition temperature of soft section of phase raise.In the present invention formula, used hyperoxia ethyl content polyether glycol, soft section contains a large amount of oxygen ethylidene groups in mutually, can dissolve all or part of urea phase, makes soft section of phase purer, and the degree that is separated is higher.Lower second-order transition temperature (50 ℃), has guaranteed that micro-pore elastomer is at room temperature elastomeric state, to such an extent as to room temperature condition can keep the high resilience of freely landing.Hyperoxia ethylidene content polyethers is introduced, and replaces traditional polytetramethylene polyether glycol, and combination material room temperature can stably stored, without crystallization, and not only save energy but also reduce particular device and loaded down with trivial details operation, the overall cost of the system that greatly reduces.
There is again the present invention in the selection of isocyanic ester, also improve, the present invention has adopted the ester modified technology of ammonia, be polyvalent alcohol elder generation and isocyanate reaction, form the end NCO performed polymer of macromolecular chain, the segmented structure finally forming is more regular, this performed polymer also can obviously improve the rebound height of landing of goods, on the other hand, the ester modified technology of ammonia can effectively be controlled viscosity, exothermic heat of reaction, the reactive behavior of reactant, be that initial reaction is unlikely to viscosity and increases too fastly, with the mobility that guarantees that material is good, can guarantee the defects such as products appearance free of pinholes.And the present invention isocyanic ester NCO used content is higher than 15wt%, and viscosity, lower than 500mPas, guarantees that goods have good mobility, avoid producing irregular pore; Have again, on the polyvalent alcohol of the ester modified isocyanic ester of ammonia is selected, the present invention is preferred higher molecular weight polyether glycol, the spalling in the time of can avoiding die sinking, guarantees the lower fraction defective of goods.Its B component isocyanic ester of traditional elastomerics way NCO content is generally lower than 10wt%, can guarantee that it has higher elasticity and other physicalies, but have B material viscosity higher (> 1000mPas), system poor fluidity, the more problem of product surface pin hole.If adopt high NCO content isocyanic ester, reduced viscosity, mobility improve, but goods closed pore is serious, the present invention is in modification MDT building-up process, preferably higher molecular weight (number-average molecular weight 6000-10000) polyether glycol, when guaranteeing the higher resilience of goods, can solve preferably the serious problem of goods closed pore, spalling in the time of can effectively avoiding die sinking, guarantees the lower fraction defective of goods simultaneously.
Polyurethane reaction ball density of the present invention is 100-600kg/m
3, in formula for a product, the water yield is less, accounts for the 0.1-0.6wt% of polymeric components, preferably 0.15-0.5wt%.The elasticity of urethane is relevant with the water yield to a certain extent.In polyurethane foam formula, the water yield is occupied very consequence to the impact of product process and physical property.Produce on the one hand carbonic acid gas as the bubble source of manufacturing polyurethane reaction ball; On the other hand, carry out chainpropagation with isocyanic ester or interlinkage reacts, thereby form urea, provide basic hardness and intensity for foam.The water yield is more, and urea is more mutually, and hard segment content improves, and reduce the rebound resilience of goods, otherwise the water yield is fewer, and urea is fewer mutually, and hard segment content is lower, can greatly improve the rebound resilience of goods.So in the present invention, the strict control of the water yield is the 0.1-0.6wt% of polymeric components, also guaranteed the resilience that goods are higher.
Fine-celled foam rebound performance of the present invention improves greatly, and the resilience that can keep freely landing in the time of 25 ℃ can reach 80%-90%, and the reaction sphere that thus prepared by micro-pore elastomer belongs to highly difficult rank, and sportsmen can practise response capacity well.
" optionally " expression is in the present invention with or without.
Embodiment
The present invention is existing to be further illustrated by following examples, but is not limited to this.
Polyol 1 dipropylene glycol is initial, the copolyether polyvalent alcohol of oxyethane and propylene oxide, ethylene oxide content 80%, molecular weight 4000, functionality 2, hydroxyl value 28.1mgKOH/g;
Polyol 2 dipropylene glycols are initial, the copolyether polyvalent alcohol of oxyethane and propylene oxide, ethylene oxide content 45%, molecular weight 7000, functionality 2, hydroxyl value 16.0mgKOH/g;
Polyol 3 dipropylene glycols and tetramethylolmethane mix initial, the copolyether polyvalent alcohol of oxyethane and propylene oxide, ethylene oxide content 55%, molecular weight 5200, functionality 3.2, hydroxyl value 34.5mgKOH/g;
Polyol 4 glycerol are initial, the copolyether polyvalent alcohol of oxyethane and propylene oxide, ethylene oxide content 80%, molecular weight 4000, functionality 3, hydroxyl value 42.1mgKOH/g;
Polyol 5 glycerol are initial, the copolyether polyvalent alcohol of oxyethane and propylene oxide, ethylene oxide content 70%, molecular weight 5500, functionality 3, hydroxyl value 30.6mgKOH/g;
Polyol 6 tetramethylolmethanes are initial, the copolyether polyvalent alcohol of oxyethane and propylene oxide, ethylene oxide content 85%, molecular weight 3200, functionality 4, hydroxyl value 70.1mgKOH/g;
Polyol 7 tetramethylolmethanes are initial, the copolyether polyvalent alcohol of oxyethane and propylene oxide, ethylene oxide content 60%, molecular weight 5000, functionality 4, hydroxyl value 44.9mgKOH/g;
Polyol 8 glycerol and tetramethylolmethane mix initial, the copolyether polyvalent alcohol of oxyethane and propylene oxide, ethylene oxide content 75%, molecular weight 4500, functionality 3.5, hydroxyl value 43.6mgKOH/g;
Polyol 9 glycerol are initial, the copolyether polyvalent alcohol of oxyethane and propylene oxide, ethylene oxide-capped copolymerization, ethylene oxide content 14%, molecular weight 4800, functionality 3, hydroxyl value 35.1mgKOH/g;
Polyol 10 glycerol are initial, the homopolymerization polyether glycol of propylene oxide, molecular weight 3500, functionality 3, hydroxyl value 48.1mgKOH/g;
Polyol 11 dipropylene glycols are initial, the homopolymerization polyether glycol of propylene oxide, molecular weight 4000, functionality 2, hydroxyl value 28.1mgKOH/g;
Polyol 12 dipropylene glycols are initial, the homopolymerization polyether glycol of propylene oxide, molecular weight 5500, functionality 2, hydroxyl value 20.4mgKOH/g;
Polyol 13 dipropylene glycols are initial, the homopolymerization polyether glycol of propylene oxide, molecular weight 7500, functionality 2, hydroxyl value 15.0mgKOH/g;
Polyol 14 glycerol are initial, the copolyether polyvalent alcohol of oxyethane and propylene oxide, ethylene oxide content 20%, molecular weight 8000, functionality 3, hydroxyl value 21.0mgKOH/g;
The concrete preparation method of Isocynate1-5 (calculating with the finished product 1000g)
The preparation of Isocynate1: add 450g diphenylmethanediisocyanate (Yantai ten thousand China in the there-necked flask that agitator, thermometer, nitrogen tube are housed, MDI-100), be heated to 60～70 ℃, then add the Polyol 9142.5g calculating, Polyol 11142.5g, Polyol 1315g.In 80 ℃ reaction 2h after, be cooled to 40 ℃ add again below 250g poly methylene poly phenyl poly isocyanate (Yantai ten thousand China, PM-200), the NCO massfraction of Isocynate1 is controlled at 21.6-22.6%;
The preparation of Isocynate2: add 400g diphenylmethanediisocyanate (Yantai ten thousand China in the there-necked flask that agitator, thermometer, nitrogen tube are housed, MDI-100), be heated to 60～70 ℃, then add the Polyol 10300g calculating, Polyol 1280g, Polyol 1420g.In 80 ℃ reaction 2h after, be cooled to 40 ℃ add again below 200g polymethylene multi-phenenyl isocyanate (Yantai ten thousand China, PM-200), the NCO massfraction of Isocynate2 is controlled at 17.8-18.8%;
The preparation of Isocynate3: (Yantai ten thousand China, MDI-100), are heated to 60～70 ℃, then add the Polyol 14500g calculating to add 300g diphenylmethanediisocyanate in the there-necked flask that agitator, thermometer, nitrogen tube are housed.In 80 ℃ reaction 2h after, be cooled to 40 ℃ add again below 200g polymethylene multi-phenenyl isocyanate (Yantai ten thousand China, PM-200), the NCO massfraction of Isocynate3 is controlled at 15.1-16.1%;
The preparation of Isocynate4: add 400g diphenylmethanediisocyanate (Yantai ten thousand China in the there-necked flask that agitator, thermometer, nitrogen tube are housed, MDI-100), be heated to 60-70 ℃, then add the Polyol 9100g calculating, Polyol 13150g.After 80 ℃ of reaction 2h, be cooled to 40 ℃ and add again below 350g polymethylene multi-phenenyl isocyanate (Yantai ten thousand China, PM-200), the NCO massfraction of Isocynate4 is 23.1-24.1%.
The preparation of Isocynate5: (Yantai ten thousand China, MDI-100), are heated to 60-70 ℃, then add the Polyol 4700g calculating to add 300g diphenylmethanediisocyanate in the there-necked flask that agitator, thermometer, nitrogen tube are housed.In 80 ℃ of reaction 2h.The NCO massfraction of Isocynate5 is 7.3-8.3%.
The preparation of embodiment 1 polyurethane reaction ball
Under normal temperature, successively above-mentioned A component raw material is put into reactor, use high speed shear agitator to stir 5 minutes, the speed of stirring is 1500 revs/min, and discharging is as System1.+ System1 and Isocynate1 are put into storage tank separately, the Isocynate1 mix and blend of the System1 of 25 ℃ and 25 ℃, stirs 8s, is poured in the mould of 35 ℃, die sinking in 7min, after room temperature is placed 30h, test mechanical property.The polyurethane reaction ball of preparing according to embodiment 1 method, density 520kg/m
3, hardness ShoreA 44, freely land resilience 84%.
The preparation of embodiment 2 polyurethane reaction balls
Under normal temperature, successively above-mentioned A component raw material is put into reactor, use high speed shear agitator to stir 5 minutes, the speed of stirring is 1500 revs/min, and discharging is as System2.System2 and Isocynate2 are put into storage tank separately, and the Isocynate1 mix and blend of the System1 of 24 ℃ and 26 ℃, stirs 7s, be poured in the mould of 35 ℃, and die sinking in 7min, after room temperature is placed 30h, test mechanical property.The polyurethane reaction ball of preparing according to embodiment 2 methods, density 450kg/m
3, hardness ShoreA 38, freely land resilience 83%.
The preparation of embodiment 3 polyurethane reaction balls
Under normal temperature, successively above-mentioned A component raw material is put into reactor, use high speed shear agitator to stir 5 minutes, the speed of stirring is 1500 revs/min, and discharging is as System3.System3 and Isocynate3 are put into storage tank separately, and the Isocynate3 mix and blend of the System3 of 23 ℃ and 26 ℃, stirs 6s, be poured in the mould of 35 ℃, and die sinking in 7min, after room temperature is placed 30h, test mechanical property.The polyurethane reaction ball of preparing according to embodiment 3 methods, density 390kg/m
3, hardness ShoreA 42, freely land resilience 82%.
The preparation of embodiment 4 polyurethane reaction balls
Under normal temperature, successively above-mentioned A component raw material is put into reactor, use high speed shear agitator to stir 5 minutes, the speed of stirring is 1500 revs/min, and discharging is as System4.System4 and Isocynate4 are put into storage tank separately, and the Isocynate4 mix and blend of the System4 of 25 ℃ and 26 ℃, stirs 9s, be poured in the mould of 35 ℃, and die sinking in 7min, after room temperature is placed 30h, test mechanical property.The polyurethane reaction ball of preparing according to embodiment 4 methods, density 340kg/m
3, hardness ShoreA 36, freely land resilience 81%.
The preparation of comparative example 1 polyurethane reaction ball
Under normal temperature, successively above-mentioned A component raw material is put into reactor, use high speed shear agitator to stir 5 minutes, the speed of stirring is 1500 revs/min, and discharging is as System5.System5 and Isocynate5 are put into storage tank separately, and the Isocynate5 mix and blend of the System5 of 25 ℃ and 26 ℃, stirs 9s, be poured in the mould of 35 ℃, and die sinking in 7min, after room temperature is placed 30h, test mechanical property.The polyurethane reaction ball of preparing according to comparative example 1 method, density 180kg/m
3, hardness ShoreA 24, freely land resilience 67%.
Table 1 fine-celled foam performance
Claims (10)
1. a polyurethane reaction ball, described reaction sphere is the microcellular polyurethane elastomer being prepared from interior raw material by comprising polymeric constituent A and pre-polymer component B, it is characterized in that: described reaction sphere foam density 100-600kg/m
3, hardness ShoreA40 ± 10, the resilience of freely landing can reach 80%-90%,
Described polymeric components A comprises:
A1,90-99.9 mass parts polyether glycol;
The frothing aid of a2,0.1-10 mass parts, comprises whipping agent, catalyzer, chainextender and mill base, and wherein catalyzer, chainextender and mill base are optional;
Described polyether glycol a1 is made by reacting ethylene oxide or is made by oxyethane and propylene oxide reaction, and its number-average molecular weight 3000-6000, oxygen ethylidene content are that 50-99wt%, average functionality are 2.1-4;
Described whipping agent is water, and the total amount of polymeric constituent A of take is benchmark, and the content of water is 0.1-0.6wt%;
Described prepolymer component B comprises:
The modification MDI of 20-50 mass parts, NCO content is 15.1-30wt%; Viscosity is 50-499mPas;
Described modification MDI is the ester modified isocyanic ester of ammonia of the NCO end-blocking that obtained by polyvalent alcohol and isocyanate reaction and the mixture of isocyanic ester; Described isocyanic ester is the mixture of diphenylmethanediisocyanate and poly methylene poly phenyl poly isocyanate arbitrary proportion; It is 2000-10000 that described polyvalent alcohol is selected from number-average molecular weight, the polyether glycol b1 of average functionality 2-3.
2. polyurethane reaction ball according to claim 1, it is characterized in that: described polyether glycol b1 is comprised of following polyethers: the polyether glycol b1 total amount of (a) take is benchmark, the number-average molecular weight 2000-6000 of 0-96wt%, and the average functionality polyether glycol b11 that is 2-3; (b) 4-100wt% number-average molecular weight 6000-10000, and average functionality is the polyether glycol b12 of 2-3.
3. polyurethane reaction ball according to claim 1, is characterized in that, it is one or more in 200 polyoxyethylene glycol that described chainextender is selected from glycol ether, dipropylene glycol, ethylene glycol, propylene glycol, BDO and number-average molecular weight.
4. polyurethane reaction ball according to claim 1, is characterized in that described catalyzer is selected from two (dimethylaminoethyl) ether, triethylenediamine, N, one or more of N-dimethylcyclohexylamine, five methyl diethylentriamine.
5. a method of preparing the polyurethane reaction ball as described in any one in claim 1-4, said method comprising the steps of:
1) polyether glycol a1, whipping agent, chainextender, mill base, catalyzer are mixed at 5-35 ℃ of temperature, then with high speed shear agitator, stir 8-15 minute, stirring velocity 1000-3000 rev/min, obtains polymeric components A;
2) by step 1) resulting polymers component A and modification MDI, in temperature, be to be uniformly mixed at 5-32 ℃, pour reaction sphere mould into, slaking, obtains polyurethane reaction ball.
6. preparation method according to claim 5, is characterized in that, said method comprising the steps of:
1) polyether glycol a1, whipping agent, chainextender, mill base, catalyzer are mixed at 15-25 ℃ of temperature, then with high speed shear agitator, stir 8-15 minute, stirring velocity 1000-3000 rev/min, obtains polymeric components A;
2) by step 1) resulting polymers component A and modification MDI, in temperature, be to be uniformly mixed at 22-28 ℃, pour reaction sphere mould into, slaking, obtains polyurethane reaction ball.
7. preparation method according to claim 5, is characterized in that: the ratio of [OH] in modification MDI in the mixture of [NCO] and described polyether glycol a1 and whipping agent is 1.1-1.4:1.
8. preparation method according to claim 7, is characterized in that: the ratio of [OH] in modification MDI in the mixture of [NCO] and described polyether glycol a1 and whipping agent is 1.15-1.38:1.
9. preparation method according to claim 5, is characterized in that: reaction sphere die temperature is 30-60 ℃; In mould, the curing time is 5-10min.
10. preparation method according to claim 9, is characterized in that: reaction sphere die temperature is 34-52 ℃; In mould, the curing time is 6-8min.
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| CN111518259B (en) * | 2020-05-06 | 2022-08-19 | 长华化学科技股份有限公司 | High-resilience polyurethane microporous elastomer and preparation method and application thereof |
| CN113651937A (en) * | 2021-08-23 | 2021-11-16 | 泾县文羽运动用品有限公司 | Production process of environment-friendly badminton liquid crystal fiberboard |
| CN114031740B (en) * | 2021-11-25 | 2023-04-07 | 北京市冰球运动协会 | Low-resilience low-density polyurethane ice ball and preparation method thereof |
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| AU2002352975A1 (en) * | 2001-11-29 | 2003-06-10 | Huntsman International Llc | Viscoelastic polyurethanes |
| CN101479309B (en) * | 2006-06-30 | 2011-10-05 | 亨茨曼国际有限公司 | Novel tennis ball |
| CN100497430C (en) * | 2006-12-06 | 2009-06-10 | 北京科聚化工新材料有限公司 | Method of preparing full MDI polyurethane slow rebound foam |
| EP2155796A1 (en) * | 2007-05-15 | 2010-02-24 | Dow Global Technologies Inc. | High resilience foams |
| CN101628965B (en) * | 2009-08-21 | 2011-07-06 | 北京科聚化工新材料有限公司 | Polyisocyanate blocked prepolymer, urethane foam and both preparation methods thereof |
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Address after: 102200 No. 5 Spark Street, Changping science and Technology Park, Beijing Applicant after: Keju Chemical New Material Co., Ltd., Beijing Applicant after: Wanhua Chemical Group Co., Ltd. Applicant after: Ningbo Wanhua Polyurethane Co., Ltd. Address before: 102200 No. 5 Spark Street, Changping science and Technology Park, Beijing Applicant before: Keju Chemical New Material Co., Ltd., Beijing Applicant before: Yantai Wanhua Polyurethane Co., Ltd. Applicant before: Ningbo Wanhua Polyurethane Co., Ltd. |
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Address after: 102200 No. 5 Spark Street, Changping science and Technology Park, Beijing Applicant after: Wanhua chemical (Beijing) Co., Ltd. Applicant after: Wanhua Chemical Group Co., Ltd. Applicant after: Wanhua Chemical (Ningbo) Co., Ltd. Address before: 102200 No. 5 Spark Street, Changping science and Technology Park, Beijing Applicant before: Keju Chemical New Material Co., Ltd., Beijing Applicant before: Wanhua Chemical Group Co., Ltd. Applicant before: Ningbo Wanhua Polyurethane Co., Ltd. |
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