CN100503762C - Macromolecule adhesive for preparing high-strength polythene weftless fabric and preparing method thereof - Google Patents
Macromolecule adhesive for preparing high-strength polythene weftless fabric and preparing method thereof Download PDFInfo
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- CN100503762C CN100503762C CNB2006100493004A CN200610049300A CN100503762C CN 100503762 C CN100503762 C CN 100503762C CN B2006100493004 A CNB2006100493004 A CN B2006100493004A CN 200610049300 A CN200610049300 A CN 200610049300A CN 100503762 C CN100503762 C CN 100503762C
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Abstract
The invention discloses a preparing method of adhesive to produce high intensity polyethylene weftless cloth, which is characterized by the following: it is a mixed solution of polystyrene natural native rubber, thickener rosin and gasoline of elasticizer, which can make high intensity polyvinyl fibre bind to weftless cloth; it possesses good resistance to impact property, which can be prepared as diverse bulletproof ware. This invention not only possesses good adhesiveness and elasticity, but also good water proof property, which possesses important usage in high molecular tip material.
Description
Technical field
The invention relates to a kind of production high-strength polyethylene that is specifically designed to and do not have liquid adhesive of latitude cloth and preparation method thereof.
Background technology
High-strength polyethylene fiber is the height-oriented most advanced and sophisticated macromolecular material of a kind of molecular chain, and it is also thinner than hair, but the intensity of its unit weight will be better than steel wire, and academia has the people to be referred to as " one dimension diamond ".The raw material for preparing this high strength fibre is the linear polyethylene of ultra-high molecular weight, being processed into the height-oriented polyethylene fibre of single direction from randomly-oriented polyethylene raw material need be through the technical process of a series of complexity, this technology is highly confidential in the world, but obtain at home in the recent period to break through, form independent intellectual property right, can produce high-strength polyethylene fiber in batches at present, realize industrialization.
From high-strength polyethylene fiber to no latitude cloth is again a technical threshold.So-called no latitude cloth just is meant without general warp parallel interlacing technology, direct fiber tiled that the blended rubber stick is bonded together and the thin layer cloth that forms.If with each layer by alternately stack of vertical mode, through compacting, adhesion-moldedly just can make board-like material.With regard to the impact resistance of no latitude cloth products, the intensity of polyethylene fibre is no doubt important, but the adhesive property of tackiness agent has played crucial effect equally, in numerous polymer composites, the cohesiveness of fiber and resin usually is the key of the final performance quality of matrix material, and reason wherein is conspicuous.As everyone knows, polyethylene is a kind of polymkeric substance that does not have polar group, height-oriented polyethylene fibre has very slick surface, this makes its very poor of surface adhesion, general commercial binder or can't play satisfied adhesive effect, can't satisfy the needs of no latitude etamine making process, therefore developing special-purpose adhesive becomes a very important job.
According to the Technology Need special adhesive three characteristics should be arranged: at first be with the polyethylene fibre surface binding property preferably to be arranged at normal temperatures, the expression behaviour of the tackiness agent of this binding property and common use is distinguishing, common binding property is to make two kinds of interfaces be in fixed " locking " state, this mode helps resisting static external force, but be unfavorable for anti-dynamic surging force, its shock proof principle of no latitude cloth as shellproof articles for use is " defeating a force with a tenderness ", be about to kinetic energy approach exhaustion in its traveling process of bullet, on flak jackets, stay the crater, do not injure human body but do not penetrate, this just requires inner jointing material still to keep cohesiveness in fiber relatively sliding process, in other words, bonding coat has certain self-healing ability after suffering outside destroy; Next is that good elasticity will be arranged, anti-ballistic materials generally all has certain elasticity, and elastic medium can transmit, dispersive stress, makes the polyethylene fibre as much as possible can be at the transient absorption external energy, make it to be transformed into heat energy, heat energy further absorbs by poly fusing; The 3rd, suitable viscosity be arranged, require the consumption of tackiness agent to be no more than 10% in the no latitude cloth making process, tackiness agent is generally made solvent with volatile gasoline, viscosity is crossed conference influences the even of coating fibers with glue, even above limiting the quantity of with glue, and viscosity too small just mean concentration cross low or molecular weight too small, can cause the on the low side or tackiness agent elasticity deficiency of efficient like this.
According to prescription provided by the invention and manufacture craft, prepared special-purpose adhesive can both meet above three requirements.
Summary of the invention
Primary technical problem to be solved by this invention provides a kind of high-strength polyethylene that is used for does not have the macromolecule adhesive that latitude cloth is produced, its compatibility advantages of simple, and easy to manufacture and use, cost is low.
Another technical problem to be solved by this invention provides the preparation method who produces above-mentioned macromolecule adhesive, and its production unit is simple, and cost is relatively low, can avoid producing pollutent in the production process.
The present invention solves the technical scheme that above-mentioned primary technical problem adopts: a kind of high-strength polyethylene that is used for does not have the macromolecule adhesive that latitude cloth is produced, it is characterized in that gasoline mixed solution for a kind of polymkeric substance, the natural rubber that contains the polystyrene modification respectively, tackifier rosin and softening agent, solute in the weight concentration of tackiness agent in 20% to 28% scope, viscosity arrives 38Pa.s scope, the natural rubber of described solute polystyrene modification at 35Pa.s, the part by weight of tackifier rosin and three kinds of compositions of softening agent is: the natural rubber weight of polystyrene modification is in 80% to 90% scope; Tackifier rosiny weight is in 8% to 15% scope; The weight of softening agent is in 2% to 5% scope.
Useful is, the natural rubber of above-mentioned polystyrene modification, the main component of natural rubber is the polyisoprene of cis, with vinylbenzene it is carried out modification and can improve its mechanical strength, when natural rubber made it to degrade with force chemistry in twin screw extruder with styrene monomer generation copolymerization, multipolymer after the generation modification, multipolymer is through water-cooled after the pelletizing, drying for standby, the temperature of above-mentioned extrusion generally is controlled at 130 ℃ to 150 ℃ scopes, the rotating speed of screw rod is controlled at per minute 140 to 180 commentaries on classics scopes, and mean residence time was 25 seconds to 35 seconds scopes.What be highly profitable is, in above-mentioned power chemical process, cinnamic weight control is being equivalent within 10% to 15% scope of natural rubber weight, and the multipolymer that is produced has reasonable elasticity and intensity, and simultaneously residual styrene monomer content is considerably less.
Useful is that described softening agent is dimixo-octyl phthalate, diisononyl phthalate or Di Iso Decyl Phthalate.
The present invention solves the technical scheme that above-mentioned another technical problem adopts: a kind of high-strength polyethylene does not have the macromolecule adhesive preparation method that the production of latitude cloth is used, it at first soaked 50 minutes to 70 minutes in gasoline under 15-25 degree temperature according to the natural rubber particle of described ratio after with modification, particle size before soaking is in the 2-4 millimeter, particle deliquescing after the swelling, size increases 3-4 doubly, at this moment the viscosity of liquid is still very little, grind to form pasty state with the particle of colloidal mill after then with swelling, polymkeric substance also can be degraded in this process, the polymkeric substance number-average molecular weight that obtains at last is generally between 60000 to 30000, accelerate greatly through the dissolution rate that grinds the post polymerization thing, improved production efficiency thus.In three phases, polymkeric substance is dissolved in the gasoline fully, and tackifier rosin and softening agent also join in the solution according to described ratio simultaneously, and the solutes content of the solution that finally obtains is between 20% to 28%, and viscosity arrives the 38Pa.s scope at 35Pa.s.Dissolution time was at 3-4 hour.
Useful is, described immersion 60 minutes, and temperature adopts room temperature, and described colloidal mill adopts split type colloidal mill, disposable particle after the swelling is ground to form pasty state.
Compared with prior art, the invention has the advantages that: special-purpose adhesive meets no latitude cloth manufacturing technique requirent fully, production unit is simple, cost is relatively low, in the entire operation process, can adopt enclosed appts, influence concentration with a large amount of volatilizations of avoiding gasoline, above-mentioned preparation method does not produce waste gas, waste water and by product, the unfavorable factor that does not have obvious contaminate environment, so do not produce pollutent in the production process, owing to adopt strong hydrophobic tackiness agent, not only bulletproof effect is better for no latitude cloth, and waterproof for a long time, soaked 1 year in water, its ballistic performance does not change, and this is more superior than making shellproof equipment with other polar macromolecule material.
Embodiment
Below in conjunction with embodiment the present invention is described in further detail.
Examples of implementation 1
The modification of natural rubber
Natural rubber adds the styrene monomer that is equivalent to rubber weight 12.5% then through being cut into small-particle, thorough mixing, and styrene monomer is absorbed by rubber fully.With a twin screw extruder rubber grain is processed, the control extrusion temperature is 140 ℃ of scopes, screw speed is in per minute 160 commentaries on classics scopes, the residence time of rubber in forcing machine should be about half a minute, during this period of time the molecular chain of rubber is ruptured by mechanical force, causes styrene polymerization simultaneously and forms multipolymer.The melt of extruding obtains solids, drying for standby at last through the pelletizing water-cooled.
The swelling of rubber grain
Mix according to the weight ratio of 1:3 in a closed container with regular gasoline through the rubber particles after the modification, after about one hour, the abundant swelling of rubber particles, size have increased 3-4 doubly, but the viscosity of liquid and little.Swollen particle and solution are poured in the funnel of the split type colloidal mill of JM-FB60 type, grind, obtain mashed prod at last with medium fineness.
The configuration of binder solution
Mashed prod after the swelling is transferred in another container that has agitator, rosin and softening agent after will smashing to pieces are in advance put into container, add a certain amount of gasoline, with the weight concentration that guarantees final solution between 20% to 28%, the weight of rubber particles, rosin and softening agent accounts for 85%, 11.5% and 3.5% of total soluble matters respectively, softening agent adopts dimixo-octyl phthalate, and its consumption increases with rosiny, remains essentially between 1:3 and the 1:4.Stir speed (S.S.) is generally changeed at per minute 1-2, continuous dissolving along with rubber, the viscosity of system also can correspondingly increase, agitator must apply bigger dynamics to guarantee invariablenes turning speed, whole dissolution process needs 3 to 4 hours, finally obtain very heavy-gravity solution, its viscosity should be at 38Pa.s to the 35Pa.s scope, the number-average molecular weight of polymkeric substance is between 60000 to 30000 in the solution, the distribution of molecular weight generally is not normal distribution, sometimes may occur bimodally, this there is no big influence to bond properties.
Examples of implementation 2
The modification of natural rubber
Natural rubber adds the styrene monomer that is equivalent to rubber weight 10% then through being cut into small-particle, thorough mixing, and styrene monomer is absorbed by rubber fully.With a twin screw extruder rubber grain is processed, the control extrusion temperature is 130 ℃ of scopes, screw speed is in per minute 180 commentaries on classics scopes, the residence time of rubber in forcing machine should be about half a minute, during this period of time the molecular chain of rubber is ruptured by mechanical force, causes styrene polymerization simultaneously and forms multipolymer.The melt of extruding obtains solids, drying for standby at last through the pelletizing water-cooled.
The swelling of rubber grain
Mix according to the weight ratio of 1:3 in a closed container with regular gasoline through the rubber particles after the modification, after about one hour, the abundant swelling of rubber particles, size have increased 3-4 doubly, but the viscosity of liquid and little.Swollen particle and solution are poured in the funnel of the split type colloidal mill of JM-FB60 type, grind, obtain mashed prod at last with medium fineness.
The configuration of binder solution
Mashed prod after the swelling is transferred in another container that has agitator, rosin and softening agent after will smashing to pieces are in advance put into container, add a certain amount of gasoline, with the weight concentration that guarantees final solution between 20% to 28%, the part by weight of rubber particles, rosin and softening agent is 80%, 8% and 2%, softening agent adopts diisononyl phthalate, and its consumption increases with rosiny, remains essentially between 1:3 and the 1:4.Stir speed (S.S.) is generally changeed at per minute 1-2, continuous dissolving along with rubber, the viscosity of system also can correspondingly increase, agitator must apply bigger dynamics to guarantee invariablenes turning speed, whole dissolution process needs 3 to 4 hours, finally obtain very heavy-gravity solution, its viscosity should be at 38Pa.s to the 35Pa.s scope, the number-average molecular weight of polymkeric substance is between 60000 to 30000 in the solution, the distribution of molecular weight generally is not normal distribution, sometimes may occur bimodally, this there is no big influence to bond properties.
Examples of implementation 3
The modification of natural rubber
Natural rubber adds the styrene monomer that is equivalent to rubber weight 15% then through being cut into small-particle, thorough mixing, and styrene monomer is absorbed by rubber fully.With a twin screw extruder rubber grain is processed, the control extrusion temperature is 150 ℃ of scopes, screw speed is in per minute 140 commentaries on classics scopes, the residence time of rubber in forcing machine should be about half a minute, during this period of time the molecular chain of rubber is ruptured by mechanical force, causes styrene polymerization simultaneously and forms multipolymer.The melt of extruding obtains solids, drying for standby at last through the pelletizing water-cooled.
The swelling of rubber grain
Mix according to the weight ratio of 1:3 in a closed container with regular gasoline through the rubber particles after the modification, after about one hour, the abundant swelling of rubber particles, size have increased 3-4 doubly, but the viscosity of liquid and little.Swollen particle and solution are poured in the funnel of the split type colloidal mill of JM-FB60 type, grind, obtain mashed prod at last with medium fineness.
The configuration of binder solution
Mashed prod after the swelling is transferred in another container that has agitator, rosin and softening agent after will smashing to pieces are in advance put into container, add a certain amount of gasoline, with the weight concentration that guarantees final solution between 20% to 28%, the part by weight of rubber particles, rosin and softening agent is 90%, 15% and 5%, softening agent adopts Di Iso Decyl Phthalate, and its consumption increases with rosiny, remains essentially between 1:3 and the 1:4.Stir speed (S.S.) is generally changeed at per minute 1-2, continuous dissolving along with rubber, the viscosity of system also can correspondingly increase, agitator must apply bigger dynamics to guarantee invariablenes turning speed, whole dissolution process needs 3 to 4 hours, finally obtain very heavy-gravity solution, its viscosity should be at 38Pa.s to the 35Pa.s scope, the number-average molecular weight of polymkeric substance is between 60000 to 30000 in the solution, the distribution of molecular weight generally is not normal distribution, sometimes may occur bimodally, this there is no big influence to bond properties.
What will illustrate at last a bit is that the weight of rubber particles, rosin and softening agent is relative weight.
Claims (7)
1, a kind of high-strength polyethylene that is used for does not have the macromolecule adhesive that latitude cloth is produced, and it is characterized in that:
It is a kind of gasoline mixed solution of polymkeric substance, the natural rubber, tackifier rosin and the softening agent that contain the polystyrene modification respectively, the weight concentration of solute in tackiness agent is in 20% to 28% scope, to the 38Pa.s scope, the part by weight of the natural rubber of described solute polystyrene modification, tackifier rosin and three kinds of compositions of softening agent is viscosity at 35Pa.s:
The natural rubber weight of polystyrene modification is in 80% to 90% scope;
Tackifier rosiny weight is in 8% to 15% scope;
The weight of softening agent is in 2% to 5% scope.
2, macromolecule adhesive according to claim 1, the natural rubber that it is characterized in that described polystyrene modification, its modification is to implement by the power chemical means in twin screw extruder, wherein cinnamic weight control is being equivalent within 10% to 15% scope of natural rubber weight, extrusion temperature is controlled at 130 ℃ to 150 ℃ scopes, screw speed is controlled at per minute 140 to 180 commentaries on classics scopes, and mean residence time was 25 seconds to 35 seconds scopes.
3, macromolecule adhesive according to claim 1 is characterized in that described softening agent is dimixo-octyl phthalate, diisononyl phthalate or Di Iso Decyl Phthalate.
4, the preparation method of the described macromolecule adhesive of a kind of claim 1 is characterized in that steps in sequence is:
A) proportionally the natural rubber particle of polystyrene modification was soaked 50 minutes to 70 minutes in gasoline to 25 degree temperature in 15 degree, particle deliquescing after the swelling, size increases 3-4 doubly;
B) grind to form pasty state with the particle of colloidal mill after with swelling;
C) under agitation polymkeric substance is dissolved in the gasoline fully, and tackifier rosin and softening agent also proportionally join in the solution simultaneously, and dissolving the required time is 3 to 4 hours;
Obtained a kind of gasoline mixed solution of polymkeric substance at last, it contains natural rubber, tackifier rosin and the softening agent of polystyrene modification respectively, the weight concentration of solute in tackiness agent is in 20% to 28% scope, to the 38Pa.s scope, the part by weight of the natural rubber of described solute polystyrene modification, tackifier rosin and three kinds of compositions of softening agent is viscosity at 35Pa.s:
The natural rubber weight of polystyrene modification is in 80% to 90% scope;
Tackifier rosiny weight is in 8% to 15% scope;
The weight of softening agent is in 2% to 5% scope.
5, the preparation method of macromolecule adhesive according to claim 4, the natural rubber that it is characterized in that described polystyrene modification, its modification is to implement by the power chemical means in twin screw extruder, wherein cinnamic weight control is being equivalent within 10% to 15% scope of natural rubber weight, extrusion temperature is controlled at 130 ℃ to 150 ℃ scopes, screw speed is controlled at per minute 140 to 180 commentaries on classics scopes, and mean residence time was 25 seconds to 35 seconds scopes.
6, the preparation method of macromolecule adhesive according to claim 5 is characterized in that described immersion 60 minutes, and temperature is a room temperature.
7, macromolecule adhesive according to claim 5 the preparation method, it is characterized in that described colloidal mill adopts split type colloidal mill, disposable particle after the swelling is ground to form pasty state.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100493004A CN100503762C (en) | 2006-02-08 | 2006-02-08 | Macromolecule adhesive for preparing high-strength polythene weftless fabric and preparing method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100493004A CN100503762C (en) | 2006-02-08 | 2006-02-08 | Macromolecule adhesive for preparing high-strength polythene weftless fabric and preparing method thereof |
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| Publication Number | Publication Date |
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| CN101016442A CN101016442A (en) | 2007-08-15 |
| CN100503762C true CN100503762C (en) | 2009-06-24 |
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| CNB2006100493004A Expired - Fee Related CN100503762C (en) | 2006-02-08 | 2006-02-08 | Macromolecule adhesive for preparing high-strength polythene weftless fabric and preparing method thereof |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102116595B (en) * | 2009-12-30 | 2013-08-21 | 宁波荣溢化纤科技有限公司 | Method for preparing stab-resistant fabric |
| CN102115651B (en) * | 2009-12-30 | 2012-05-23 | 宁波荣溢化纤科技有限公司 | Adhesive used for preparing stab-resistant fabrics |
| CN104999748B (en) * | 2015-06-02 | 2017-03-01 | 常熟市永利坚新材料有限公司 | A kind of manufacture method of the soft laminated cloth of shock resistance |
| CN106350943A (en) * | 2016-08-30 | 2017-01-25 | 江苏领瑞新材料科技有限公司 | Modified impact-resistant composite weftless cloth and manufacturing method thereof |
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Granted publication date: 20090624 Termination date: 20120208 |