CN105924605A - Manufacturing method of elastic nylon tire inner supporting body - Google Patents
Manufacturing method of elastic nylon tire inner supporting body Download PDFInfo
- Publication number
- CN105924605A CN105924605A CN201610361381.5A CN201610361381A CN105924605A CN 105924605 A CN105924605 A CN 105924605A CN 201610361381 A CN201610361381 A CN 201610361381A CN 105924605 A CN105924605 A CN 105924605A
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- CN
- China
- Prior art keywords
- caprolactam
- preparation
- polyurethane prepolymer
- component
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/4266—Polycondensates having carboxylic or carbonic ester groups in the main chain prepared from hydroxycarboxylic acids and/or lactones
- C08G18/4269—Lactones
- C08G18/4277—Caprolactone and/or substituted caprolactone
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/2805—Compounds having only one group containing active hydrogen
- C08G18/285—Nitrogen containing compounds
- C08G18/2855—Lactams
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention discloses a manufacturing method of an elastic nylon tire inner supporting body. The manufacturing method comprises the following steps that 1, dehydration of caprolactam is performed; 2, a caprolactam end capped polyurethane prepolymer is prepared; 3, catalyst components are prepared; 4, mixed casting is performed: the catalyst components are added to a casting machine A material storage tank, degassing is performed at the temperature of 100-140 DEG C and under the pressure lower than or equal to 1000 pa for 10 minutes, and circulation is performed under a nitrogen atmosphere for standby application; the two components are mixed by using a casting machine according to the mass ratio of 1-1.5 to 1, the mixture is cast into a mold of the temperature of 140-180 DEG C and then is put in a drying oven of the temperature of 140-180 DEG C to perform curing reaction for 4-8 hours, and demolding and machining are performed; 5, after curing is completed, machining is performed to obtain a finished product. The manufacturing method is simple and practical, tedious post-treatment process is omitted, the production rate is high, the production costs are, and the production efficiency is high.
Description
Technical field
The present invention relates to the manufacturing technology of a kind of stretchy nylon internal supporting body for tyre, more specifically refer to, for more
The manufacture method of the tire inner support that wild car uses.
Background technology
The raising required vehicle safety along with people, Runflat type tire is the most various
Vehicle (particularly security car and military vehicle) is selected.As realizing leakage of tyre wheeled function
Vitals, inner supporting body is currently mainly divided into two big classes:
One, the supporter (rubber, polyurethane elastomer etc.) of elastomer material: due to this kind of material
Good elasticity, in the case of leakage of tyre, this type of supporter can meet vehicle various road surfaces (paving
Dress road, cross-country road etc.) on continue to travel, and it is the most handling to make vehicle still have.But this type of supports
The quality of body is bigger, it is impossible to meet the light-weighted demand of vehicle.
Two, the maximum feature of light plastic supporter (nylon, UHMWPE etc.): such supporter is firm
Property strong, component can make frivolous structure on the basis of meeting bearing requirements.And the density of this kind of material
Less only 0.9-1.15g/cm3, therefore the quality of such supporter can greatly reduce.But it is too strong
Rigidity causes its poor impact toughness, buffering damping capaicty poor, it is impossible to meet under leakage of tyre state, vehicle
Non-road of mating formation (such as cross-country road, broken stone road etc.) continue travel；At present only strong to the impact of material
Degree requires to use on relatively low non-off-road vehicle.
Summary of the invention
The invention aims to i.e. meet wanting of the non-paved road impact property higher to supporter
Ask, it is provided that a kind of novel elastic nylon inner supporting body.
The manufacture method of the present invention a kind of stretchy nylon internal supporting body for tyre, is carried out as steps described below:
1. the dehydration of caprolactam: caprolactam at 100-150 DEG C, vacuum dehydration 2 under 600pa absolute pressure
Hour, to water content less than 100ppm；
2. the preparation (abbreviation B component) of the base polyurethane prepolymer for use as of caprolactam blocking:
A. the preparation of base polyurethane prepolymer for use as: prepare by the customary preparation methods of base polyurethane prepolymer for use as, performed polymer
Middle diisocyanate with the mol ratio of polymer polyatomic alcohol is: 4-12:1；
Wherein polymer polyatomic alcohol be molecular weight be poly-tetrahydrochysene furosemide feeding glycol or the polyadipate second of 500-3000
Diol ester glycol or polycaprolactone glycol, diisocyanate is 3, and 3 '-dimethyl-4,4 '-biphenyl two is different
Cyanate or 1,5 naphthalene diisocyanates or 4,4-dicyclohexyl methyl hydride diisocyanate or hexa-methylene two
Isocyanates；
B. the preparation of distribution of low molecular weight base polyurethane prepolymer for use as: by pre-for the polyurethane of preparation in above-mentioned a. step
Aggressiveness is placed in short-path evaporator, at 60-100 DEG C, under 60pa absolute pressure, by two wherein free isocyanic acids
Ester monomer removal also reclaims, and obtains distribution of low molecular weight base polyurethane prepolymer for use as；
C. the preparation of the base polyurethane prepolymer for use as of caprolactam blocking: by the low molecule of preparation in above-mentioned b. step
The caprolactam of the de-good water that the base polyurethane prepolymer for use as of amount distribution is prepared with above-mentioned steps 1 in proportion exists
At 100-130 DEG C, nitrogen atmosphere reacts 1-2 hour；Caprolactam and the polyurethane of distribution of low molecular weight
The specific mass of performed polymer is: 1-3:1；
3. the preparation (abbreviation component A) of catalytic component: oneself of de-good water prepared by above-mentioned steps 1
Lactams in proportion with catalyst at 100-130 DEG C, in nitrogen atmosphere, hybrid reaction 0.5 hour, takes off
The caprolactam of water mass ratio with catalyst in proportion is: 100:2-5, and described catalyst is lithium alkylide,
The mixture of sodium hydride or sodium caprolactam and caprolactam；
4. mixing cast: in the component A of preparation adds casting machine A storage tank in above-mentioned steps 3,
After temperature is 100～140 DEG C, deaerates 10 minutes under conditions of pressure≤1000pa, under nitrogen atmosphere
Circulate standby；In in above-mentioned steps 2, the B component of preparation adds the B storage tank of casting machine, in temperature
Be 100～140 DEG C, deaerate 30 minutes under conditions of pressure≤1000pa after, circulate standby under nitrogen atmosphere
With；It is that 1-1.5:1 mixes and is poured into temperature and is with casting machine by component A and B component example in mass ratio
In 140～180 DEG C of moulds, then to be placed in temperature be curing reaction 4-8 hour in 140～180 DEG C of baking ovens；
5. the demoulding and machining: after solidification terminates, be removed from the molds by goods while hot, by figure after cooling
Paper requires that carrying out machining had both obtained finished product.
The invention have the advantage that preparation method is simple and practical, eliminate loaded down with trivial details last handling process, make
Rate is high, and production cost is low, and production efficiency is high, compares to traditional handicraft cost and reduces by 10%, and the operation cycle subtracts
Few 30%.
Prepared stretchy nylon inner supporting body has a characteristic that
Density :≤1.10g/cm3
Hardness: 68 ± 2Shore D
Hot strength: >=50Mpa
Percentage elongation: >=400%
Notch impact strength: >=80KJ/m2
Low temperature impact strength (-40 DEG C): >=20KJ/m2。
Detailed description of the invention
Embodiment 1.
One, the dehydration of caprolactam:
Caprolactam monomer, puts in reactor, at 135 DEG C, under 600pa absolute pressure, and vacuum dehydration 1
Hour standby.
Two, the preparation of the base polyurethane prepolymer for use as of caprolactam blocking:
1. the preparation of base polyurethane prepolymer for use as:
Weigh polycaprolactone glycol 100 mass parts that number average molecular weight is 2000, put in reactor,
115 DEG C, under 600pa absolute pressure, vacuum dehydration 2 hours, it is cooled to 80 DEG C, is added into depositing
Have in the reactor of hexamethylene diisocyanate of 84 mass parts, in 80 DEG C, nitrogen atmosphere
Under, stirring reaction 2.5 hours, continues vacuum outgas 0.5 hour under 80 DEG C of 1000pa residual voltages.
2. the preparation of distribution of low molecular weight base polyurethane prepolymer for use as: by the polyurethane of preparation in above-mentioned steps 1.
Performed polymer puts in short-path evaporator, 80 DEG C, under 60pa absolute pressure, and six methylenes that removing is free
Group diisocyanate monomer, the NCO% to performed polymer is 3.6.
3. the preparation of the base polyurethane prepolymer for use as of caprolactam blocking: weigh in above-mentioned steps 2. the low of preparation
Base polyurethane prepolymer for use as 20 mass parts of molecular weight distribution and above-mentioned steps one, in oneself of de-good water
Lactams 30 mass parts, at 130 DEG C, is reacted 1 hour in nitrogen atmosphere.
Three, the preparation (abbreviation component A) of catalytic component: weigh above-mentioned steps one, in de-good water
Caprolactam 47.5 mass parts and catalyst (mixture of sodium hydride and caprolactam, quality
Than 5:95) 2.5 mass parts at 130 DEG C, hybrid reaction 0.5 hour in nitrogen atmosphere.
Four, mixing cast: the component A of above-mentioned steps three, middle preparation is added casting machine A storing
In tank, after temperature is 135 DEG C, deaerates 10 minutes under conditions of pressure≤1000pa, nitrogen
Circulate standby under atmosphere, the B component of above-mentioned steps two, middle preparation is added the B storing of casting machine
In tank after temperature is for being 135 DEG C in temperature, deaerating 30 minutes under conditions of pressure≤1000pa,
Circulate standby under nitrogen atmosphere, be that 1:1 mixes with casting machine by component A and B component example in mass ratio
Merge that to be poured into temperature be in 160 DEG C of moulds, then to be placed in temperature be curing reaction 6 in 160 DEG C of baking ovens
Hour.
Five, the demoulding and machining: after solidification terminates, while hot goods are removed from the molds, cooling
After carry out by drawing machining both finished product.
The performance of resulting product is as follows:
Density: 1.08g/cm3
Hardness: 67Shore D
Hot strength: 52.3Mpa
Percentage elongation: 500%
Notch impact strength: 103KJ/m2
Low temperature impact strength (-40 DEG C): 30KJ/m2。
Embodiment 2.
One, the dehydration of caprolactam:
Caprolactam monomer, puts in reactor.At 135 DEG C, under 600pa absolute pressure, vacuum dehydration 1
Hour standby.
Two, the preparation of the base polyurethane prepolymer for use as of caprolactam blocking:
1. the preparation of base polyurethane prepolymer for use as:
Weigh polytetrahydrofuran diol 100 mass parts that number average molecular weight is 2000, put into reactor
In, 115 DEG C, under 600pa absolute pressure, vacuum dehydration 2 hours.It is cooled to 80 DEG C, is added
Enter and have the 3 of 132 mass parts, 3 '-dimethyl-4, the reaction of 4 '-biphenyl diisocyanate
In still, in 95 DEG C, under nitrogen atmosphere, stirring reaction 1.5 hours.80 DEG C, 1000pa is residual
Pressure continues vacuum outgas 0.5 hour.
2. the preparation of distribution of low molecular weight base polyurethane prepolymer for use as: by the polyurethane of preparation in above-mentioned steps 1.
Performed polymer puts in short-path evaporator, 100 DEG C, under 60pa absolute pressure, removes free 3,3 '
-dimethyl-4,4 '-biphenyl diisocyanate monomer, the NCO% to performed polymer is 3.32.
3. the preparation of the base polyurethane prepolymer for use as of caprolactam blocking: weigh in above-mentioned steps 2. the low of preparation
Base polyurethane prepolymer for use as 25 mass parts of molecular weight distribution and above-mentioned steps one, in oneself of de-good water
Lactams 25 mass parts, at 130 DEG C, is reacted 1 hour in nitrogen atmosphere.
Three, the preparation (abbreviation component A) of catalytic component: weigh above-mentioned steps one, in de-good water
Caprolactam 47 mass parts and catalyst (sodium caprolactam and the mixture of caprolactam, quality
Ratio: 10:90) 3 mass parts are at 130 DEG C, hybrid reaction 0.5 hour in nitrogen atmosphere.
Four, mixing cast: the component A of above-mentioned steps three, middle preparation is added casting machine A storing
In tank, after temperature is 135 DEG C, deaerates 10 minutes under conditions of pressure≤1000pa, nitrogen
Circulate standby under atmosphere.The B component of above-mentioned steps two, middle preparation is added the B storing of casting machine
In tank after temperature is for being 135 DEG C in temperature, deaerating 30 minutes under conditions of pressure≤1000pa,
Circulate standby under nitrogen atmosphere.It is that 1:1 mixes with casting machine by component A and B component example in mass ratio
Merge that to be poured into temperature be in 160 DEG C of moulds, then to be placed in temperature be curing reaction 6 in 160 DEG C of baking ovens
Hour.
Five, the demoulding and machining: after solidification terminates, while hot goods are removed from the molds, press after cooling
Drawing requirement carries out machining and had both obtained finished product.
The performance of resulting product is as follows:
Density: 1.10g/cm3
Hardness: 70Shore D
Hot strength: 57.5Mpa
Percentage elongation: 420%
Notch impact strength: 87KJ/m2
Low temperature impact strength (-40 DEG C): 25KJ/m2。
Claims (1)
1. a manufacture method for stretchy nylon internal supporting body for tyre, is characterized in that, enters as steps described below
OK:
A. the dehydration of caprolactam: caprolactam is at 100-150 DEG C, and under 600pa absolute pressure, vacuum dehydration 2 is little
Time, to water content less than 100ppm；
B. the preparation of the base polyurethane prepolymer for use as of caprolactam blocking, abbreviation B component:
A. the preparation of base polyurethane prepolymer for use as: prepare by the customary preparation methods of base polyurethane prepolymer for use as, performed polymer
Middle diisocyanate with the mol ratio of polymer polyatomic alcohol is: 4-12:1；
Wherein polymer polyatomic alcohol be molecular weight be poly-tetrahydrochysene furosemide feeding glycol or the polyadipate second of 500-3000
Diol ester glycol or polycaprolactone glycol, diisocyanate is 3, and 3 '-dimethyl-4,4 '-biphenyl two is different
Cyanate or 1,5 naphthalene diisocyanates or 4,4-dicyclohexyl methyl hydride diisocyanate or hexa-methylene two
Isocyanates；
B. the preparation of distribution of low molecular weight base polyurethane prepolymer for use as: by pre-for the polyurethane of preparation in above-mentioned a. step
Aggressiveness is placed in short-path evaporator, at 60-100 DEG C, under 60pa absolute pressure, by two wherein free isocyanic acids
Ester monomer removal also reclaims, and obtains distribution of low molecular weight base polyurethane prepolymer for use as；
C. the preparation of the base polyurethane prepolymer for use as of caprolactam blocking: by the low molecule of preparation in above-mentioned b. step
The caprolactam of the de-good water that the base polyurethane prepolymer for use as of amount distribution is prepared with above-mentioned steps A in proportion exists
At 100-130 DEG C, nitrogen atmosphere reacts 1-2 hour；Caprolactam and the polyurethane of distribution of low molecular weight
The specific mass of performed polymer is: 1-3:1；
C. the preparation of catalytic component, abbreviation component A: the own interior acyl of de-good water prepared by above-mentioned steps A
Amine in proportion with catalyst at 100-130 DEG C, hybrid reaction 0.5 hour in nitrogen atmosphere, de-good water
Caprolactam mass ratio with catalyst in proportion is: 100:2-5, and described catalyst is lithium alkylide, hydrogenation
The mixture of sodium or sodium caprolactam and caprolactam；
D. cast is mixed: in the component A of preparation adds casting machine A storage tank in above-mentioned steps C,
Temperature is 100～140 DEG C, deaerate 10 minutes under conditions of pressure≤1000pa after, follow under nitrogen atmosphere
Ring is standby；In in above-mentioned steps B, the B component of preparation adds the B storage tank of casting machine, in temperature it is
100～140 DEG C, deaerate 30 minutes under conditions of pressure≤1000pa after, circulate standby under nitrogen atmosphere；
With casting machine by component A and B component example in mass ratio be 1-1.5:1 mix and be poured into temperature be 140～
In 180 DEG C of moulds, then to be placed in temperature be curing reaction 4-8 hour in 140～180 DEG C of baking ovens；
E. the demoulding and machining: after solidification terminates, be removed from the molds by goods while hot, by figure after cooling
Paper requires that carrying out machining had both obtained finished product.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610361381.5A CN105924605B (en) | 2016-05-26 | 2016-05-26 | A kind of manufacture method of stretchy nylon internal supporting body for tyre |
Applications Claiming Priority (1)
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| CN201610361381.5A CN105924605B (en) | 2016-05-26 | 2016-05-26 | A kind of manufacture method of stretchy nylon internal supporting body for tyre |
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| CN105924605A true CN105924605A (en) | 2016-09-07 |
| CN105924605B CN105924605B (en) | 2018-05-15 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111285993A (en) * | 2020-03-09 | 2020-06-16 | 江苏科技大学 | Preparation method of high-fluidity polyamide 6 elastomer |
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| CN101195706A (en) * | 2006-12-09 | 2008-06-11 | 中国科学院兰州化学物理研究所 | Method for producing polyurethane toughness-reinforcing cast form nylon composite material |
| CN102399357A (en) * | 2011-09-29 | 2012-04-04 | 四川大学 | Method for preparing multi-block nylon polyurethane elastomer |
| CN103289381A (en) * | 2013-06-20 | 2013-09-11 | 四川大学 | In-situ reinforced and toughened MC nylon 6 composite material and preparation method thereof |
| CN105273183A (en) * | 2015-11-20 | 2016-01-27 | 中南林业科技大学 | Composite friction material and preparation method and device thereof |
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2016
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101195706A (en) * | 2006-12-09 | 2008-06-11 | 中国科学院兰州化学物理研究所 | Method for producing polyurethane toughness-reinforcing cast form nylon composite material |
| CN102399357A (en) * | 2011-09-29 | 2012-04-04 | 四川大学 | Method for preparing multi-block nylon polyurethane elastomer |
| CN103289381A (en) * | 2013-06-20 | 2013-09-11 | 四川大学 | In-situ reinforced and toughened MC nylon 6 composite material and preparation method thereof |
| CN105273183A (en) * | 2015-11-20 | 2016-01-27 | 中南林业科技大学 | Composite friction material and preparation method and device thereof |
Non-Patent Citations (1)
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111285993A (en) * | 2020-03-09 | 2020-06-16 | 江苏科技大学 | Preparation method of high-fluidity polyamide 6 elastomer |
| CN111285993B (en) * | 2020-03-09 | 2022-01-28 | 江苏科技大学 | Preparation method of high-fluidity polyamide 6 elastomer |
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| CN105924605B (en) | 2018-05-15 |
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