CN103834329B - A kind of halogen-free environmental sizing agent and preparation method thereof - Google Patents
A kind of halogen-free environmental sizing agent and preparation method thereof Download PDFInfo
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- CN103834329B CN103834329B CN201410099237.XA CN201410099237A CN103834329B CN 103834329 B CN103834329 B CN 103834329B CN 201410099237 A CN201410099237 A CN 201410099237A CN 103834329 B CN103834329 B CN 103834329B
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Abstract
The invention discloses a kind of halogen-free environmental sizing agent and preparation method thereof, the composition of raw materials of described halogen-free environmental sizing agent is made up of the material of following mass percentage: the polyacrylate pressure-sensitive of 30% ~ 40%, the titanium dioxide of 1% ~ 3%, the fire retardant of 15% ~ 25%, antimonous oxide, the toner of 2% ~ 3%, the solidifying agent of 0.5% ~ 1.5% of 1% ~ 2%; Surplus is ethyl acetate.Sizing agent cohesive force prepared by this case is strong, Halogen, low toxicity, and excellent fireproof performance, and within 10 seconds, from putting out, can match in excellence or beauty halogenated flame retardant.This preparation method is simple, and added ingredients is few, and not containing auxiliary agents such as flow agent, anti-sludging agent, defoamer, emulsifying agents, production cost is low, and preparation condition is gentle, environmental protection.
Description
Technical field
The present invention relates to sizing agent field, particularly a kind of halogen-free environment-friendly flame-proof sizing agent and preparation method thereof.
Background technology
From between early 1950s so far more than 60 year, particularly between early 1980s so far about 30 years, fire retardant (FR) and flame retarded polymeric material have played important effect reducing in the life and property loss that fire causes.Current, total consumption of global FR is only second to softening agent and occupies second in all types of plastic auxiliary agent.
In recent years, the annual average rate of increase of Chinese fire retardant turnout was estimated to reach 15% ~ 20%, far away higher than the level in the whole world 3% ~ 4%.Within 2010, Plastics in China goods output is 5830.38 ten thousand tons, 20% and the fire retardant usage ratio 10% accounting for plastics by flame retardant plastics calculates, within 2010, domestic fire retardant industry potential market scale is at about 1,170,000 tons, and within 2011, domestic fire retardant industry potential market scale is at about 980,000 tons.China's combustion agent all there is gap with developed country in kind or quantitatively, and DEVELOPMENT PROSPECT is wide, should improve exploitation innovation ability, promote fire retardant industry towards environmental protection, lowly to poison, the future development of high efficiency, multifunction.
The kind of domestic fire retardant and consumption still based on organic fire-retardant, although and the most frequently used halogenated flame retardant has the unrivaled high efficiency of other fire retardants series, it is very important to the harm of environment and people.Environmental issue is the focus that auxiliary agent development and application business pays close attention to, so adjusting the product structure of fire retardant both at home and abroad always, strengthens the exploitation of Efficient environment-friendlyflame flame retardant.Halogen, low cigarette, low-poison and combustion-resisting agent are the targets that people pursue always, and people show very high enthusiasm to the non-halogen exploitation of fire retardant in recent years, have dropped into very large strength, and have achieved considerable achievement.
Summary of the invention
The invention provides a kind of compound halogen-free environmental sizing agent and preparation method thereof, this preparation method is simple, and added ingredients is few, and cost is low, and working condition is gentle, environmental protection.The sizing agent that present method is made, Halogen, low toxicity, the halogenated flame retardant and flame retardant effect can match in excellence or beauty.
Technical scheme of the present invention is summarized as follows:
A kind of halogen-free environmental sizing agent, its composition of raw materials is made up of the material of following mass percentage:
Wherein, the solid content of described polyacrylate pressure-sensitive is 45%, surplus is ethyl acetate, and the solids component of described polyacrylate pressure-sensitive is formed by the material random copolymerization of following mass percentage: the Isooctyl methacrylate of 63.3%, the methyl methacrylate of 4.9% and 31.8% hydroxyethyl methylacrylate;
Described fire retardant is made up of the material of following mass percentage: four-(2, the 6-xylyl) resorcinol diphosphate of 34%, the tetraphenyl resorcinol diphosphate of 42%, the ammonium nitrate of 3% and the graphite of 21%; Wherein, the particle diameter of described graphite is 300 ~ 500 orders;
Described solidifying agent is selected from aminoethyl piperazine, isophorone diamine, triethylene tetramine, m-xylene diamine, methylene-bis phenylenediamine or its combination.Toner is generally natural colored mineral powder, and as titanium ultramarine powder, the selection of toner can be selected according to actual needs, and specific restriction is not done in this case.
A preparation method for halogen-free environmental sizing agent, comprises the following steps:
Step 1) ground slurry: take titanium dioxide, fire retardant, antimonous oxide, toner and ethyl acetate respectively by composition of raw materials according to claim 1 and they are put into reaction vessel, add the zirconium oxide bead with titanium dioxide, fire retardant, antimonous oxide and toner same volume accumulated amount simultaneously, with mechanical stirring device with the rotating speed agitation grinding 3 hours of 400 ~ 800 revs/min, add a Vltrasonic device while stirring in the outside of described reaction vessel and ultrasonication is carried out to the material in reaction vessel;
Step 2) fineness test: take out step 1) grinding gained slurry, be placed on fineness plate and detect fineness, if slurry particle diameter≤3 μm, then carry out next step operation; If slurry particle diameter > 3 μm, then continue grinding until slurry particle diameter≤3 μm;
Step 3) finished product preparation: put into another reaction vessel after having taken polyacrylate pressure-sensitive by composition of raw materials according to claim 1, polyacrylate pressure-sensitive is stirred with the rotating speed of 1000 revs/min with mechanical stirring device, step 1 is added subsequently in the polyacrylate pressure-sensitive in stirring) grinding gained slurry, stirring is continued 5 minutes after interpolation, this reaction vessel is put into after having taken solidifying agent by composition of raw materials according to claim 1 subsequently, stir 20 ~ 30 minutes, namely obtain described halogen-free environmental sizing agent.
Preferably, the preparation method of described halogen-free environmental sizing agent, step 1) gained slurry is accomplished to from preparation the timed interval be added into polyacrylate pressure-sensitive and is no more than 20 minutes.
The invention has the beneficial effects as follows: sizing agent cohesive force prepared by this case is strong, Halogen, low toxicity, and excellent fireproof performance, within 10 seconds, from putting out, can match in excellence or beauty halogenated flame retardant.This preparation method is simple, and added ingredients is few, and not containing auxiliary agents such as flow agent, anti-sludging agent, defoamer, emulsifying agents, production cost is low, and preparation condition is gentle, environmental protection.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, can implement according to this with reference to specification sheets word to make those skilled in the art.
A kind of halogen-free environmental sizing agent, its composition of raw materials is made up of the material of following mass percentage:
Wherein, polyacrylate pressure-sensitive is the main body of sizing agent, and its performance difference directly decides the clinging power of this binding agent.In this case, the solid content of polyacrylate pressure-sensitive is 45%, and surplus is ethyl acetate solvent.Following table is the clinging power corresponding to the solids component of polyacrylate pressure-sensitive and viscosity ratio pair that are obtained by the monomer random copolymerization containing different mass per-cent:
Table one
*, in table, A represents Isooctyl methacrylate, and B represents methyl methacrylate, and C represents hydroxyethyl methylacrylate.
This case organizes screening to the monomer in the solids component of polyacrylate pressure-sensitive more, a representative part is only listed in table one, from table one, we are not difficult to find out, if consider viscosity and clinging power two parameters, its optimum monomer component proportioning is: the Isooctyl methacrylate of 63.3%, the methyl methacrylate of 4.9% and 31.8% hydroxyethyl methylacrylate.If viscosity is excessive, the Painting effect of sizing agent can be affected; Viscosity is too little, can affect the drying and shaping effect of sizing agent.Isooctyl methacrylate is soft monomer, is mainly used in the pliability and the viscosity that improve pressure sensitive adhesive; Methyl methacrylate is hard monomer, is mainly used in the second-order transition temperature and the integral hardness that improve pressure sensitive adhesive; Hydroxyethyl methylacrylate is function monomer, is mainly used in improving solvent resistance and providing cross-linking set.When monomer random copolymerization, if polymerization effect is undesirable, 0.5 ~ 2g benzoyl peroxide (BPO) preferably can be added as initiator.
Following table is the flame retardant properties contrast containing the fire retardant material of different mass percent composition:
Table two
| Experiment 1 | Experiment 2 | Experiment 3 | Experiment 4 | Experiment 5 | Experiment 6 | Experiment 7 | |
| D | 100％ | - | 25％ | 34％ | 35％ | 34％ | 35％ |
| E | - | 100％ | 25％ | 41.5％ | 35％ | 42％ | 35％ |
| F | - | - | 25％ | 3％ | 5％ | 3％ | 5％ |
| G | - | - | 25％ | 20％ | 25％ | 21％ | 24％ |
| H | - | - | - | 1.5％ | - | - | 1％ |
| From fire from putting out | 13s | 14s | 12s | 9s | 12s | 10s | 10s |
*, in table, D represents 41 (2,6-xylyl) resorcinol diphosphate, and E represents tetraphenyl resorcinol diphosphate, and F represents ammonium nitrate, and G represents graphite, and H represents antimonous oxide.
Fire retardant is generally by such as heat-absorbing action, covering effect, suppress radical chain reaction, suffocating etc. of non-flammable gas plays its fire retardation.And polycomponent composite flame-retardant agent popular at present reaches fire-retardant object by some mechanism actings in conjunction.Antimonous oxide and titanium dioxide all belong to fire retarding synergist, and normal and other fire retardants, smoke suppressor use, can produce synergistic effect between each component.Titanium dioxide in antimonous oxide and titanium dioxide, at the burning initial stage, is first melting, forms protective membrane completely cut off air at material surface, by inner thermo-negative reaction, reduces temperature of combustion.Antimonous oxide is vaporized at high operating temperatures, dilutes oxygen concn in air, thus plays fire retardation.
The component screening of this case to fire retardant has some, and only list a representative part in table two, from table two, we are not difficult to find out, with the addition of antimonous oxide as fire retarding synergist after, obviously shortening from fiery self-extinguishing time of fire retardant.Simple from each component proportion of fire retardant, its optimum combination is: four-(2, the 6-xylyl) resorcinol diphosphate of 34wt%, the tetraphenyl resorcinol diphosphate of 42wt%, the ammonium nitrate of 3wt% and the graphite of 21wt%; Wherein, the particle diameter of graphite is preferably 300 ~ 500 orders.
Solidifying agent is selected from aminoethyl piperazine, isophorone diamine, triethylene tetramine, m-xylene diamine, methylene-bis phenylenediamine or its combination.
The preparation method of this halogen-free environmental sizing agent, comprises the following steps:
Step 1) ground slurry: take titanium dioxide respectively by above-mentioned composition of raw materials, fire retardant, antimonous oxide, they are also put into reaction vessel by toner and ethyl acetate, add and titanium dioxide simultaneously, fire retardant, the zirconium oxide bead of antimonous oxide and toner same volume accumulated amount, the particle diameter of zirconium oxide bead is 1 ~ 2mm, with mechanical stirring device with the rotating speed agitation grinding 3 hours of 400 ~ 800 revs/min, add a Vltrasonic device in the outside of described reaction vessel while stirring and ultrasonication is carried out to the material in reaction vessel, to improve mill efficiency and grinding precision,
Step 2) fineness test: take out step 1) grinding gained slurry, be placed on fineness plate and detect fineness, if slurry particle diameter≤3 μm, then carry out next step operation; If slurry particle diameter > 3 μm, then continue grinding until slurry particle diameter≤3 μm;
Step 3) finished product preparation: put into another reaction vessel after having taken polyacrylate pressure-sensitive by composition of raw materials according to claim 1, polyacrylate pressure-sensitive is stirred with the high rotating speed of 1000 revs/min with mechanical stirring device, a small amount of diluted ethyl acetate is optionally added when stirring, step 1 is added subsequently in the polyacrylate pressure-sensitive in stirring) grinding gained slurry, attentional manipulation speed time reinforced, prevent from spilling, slurry is added under so high rotating speed, be exactly mainly prevent slurry reunite and coated by polyacrylate pressure-sensitive, stirring is continued 5 minutes after interpolation, this reaction vessel is put into after having taken solidifying agent by composition of raw materials according to claim 1 subsequently, stir 20 ~ 30 minutes, namely described halogen-free environmental sizing agent is obtained.
After slurry prepares, just should at short notice with polyacrylate pressure-sensitive mix.Owing to not adding dispersion agent in slurry, the auxiliary agents such as anti-sludging agent, after ground slurry leaves standstill, again will soon precipitate, reunite, and after current reunion, the slurry of grinding can be reunited together in more stable mode, not easily opens, therefore, step 1) gained slurry is accomplished to from preparation the timed interval be added into polyacrylate pressure-sensitive should more than 20 minutes.
Below concrete composition of raw materials and the flame retardant properties parameter of different embodiment:
Table three
Although embodiment of the present invention are open as above, but it is not restricted to listed in specification sheets and embodiment utilization, it can be applied to various applicable the field of the invention completely, for those skilled in the art, can easily realize other amendment, therefore do not deviating under the universal that claim and equivalency range limit, the present invention is not limited to specific details.
Claims (3)
1. a halogen-free environmental sizing agent, is characterized in that, the composition of raw materials of described halogen-free environmental sizing agent is made up of the material of following mass percentage:
Surplus is ethyl acetate;
Wherein, the solid content of described polyacrylate pressure-sensitive is 45%, surplus is ethyl acetate, and the solids component of described polyacrylate pressure-sensitive is formed by the material random copolymerization of following mass percentage: the Isooctyl methacrylate of 63.3%, the methyl methacrylate of 4.9% and 31.8% hydroxyethyl methylacrylate;
Described fire retardant is made up of the material of following mass percentage: four-(2, the 6-xylyl) resorcinol diphosphate of 34%, the tetraphenyl resorcinol diphosphate of 42%, the ammonium nitrate of 3% and the graphite of 21%; Wherein, the particle diameter of described graphite is 300 ~ 500 orders;
Described solidifying agent is selected from aminoethyl piperazine, isophorone diamine, triethylene tetramine, m-xylene diamine, methylene-bis phenylenediamine or its combination;
Particle diameter≤3 μm of described titanium dioxide, fire retardant, antimonous oxide and toner.
2. a preparation method for halogen-free environmental sizing agent, is characterized in that, comprises the following steps:
Step 1) ground slurry: take titanium dioxide, fire retardant, antimonous oxide, toner and ethyl acetate respectively by composition of raw materials according to claim 1 and they are put into reaction vessel, add the zirconium oxide bead with titanium dioxide, fire retardant, antimonous oxide and toner same volume accumulated amount simultaneously, with mechanical stirring device with the rotating speed agitation grinding 3 hours of 400 ~ 800 revs/min, add a Vltrasonic device while stirring in the outside of described reaction vessel and ultrasonication is carried out to the material in reaction vessel;
Step 2) fineness test: take out step 1) grinding gained slurry, be placed on fineness plate and detect fineness, if slurry particle diameter≤3 μm, then carry out next step operation; If slurry particle diameter > 3 μm, then continue to be ground to slurry particle diameter≤3 μm;
Step 3) finished product preparation: put into another reaction vessel after having taken polyacrylate pressure-sensitive by composition of raw materials according to claim 1, polyacrylate pressure-sensitive is stirred with the rotating speed of 1000 revs/min with mechanical stirring device, step 1 is added subsequently in the polyacrylate pressure-sensitive in stirring) grinding gained slurry, stirring is continued 5 minutes after interpolation, this reaction vessel is put into after having taken solidifying agent by composition of raw materials according to claim 1 subsequently, stir 20 ~ 30 minutes, namely obtain described halogen-free environmental sizing agent.
3. the preparation method of halogen-free environmental sizing agent according to claim 2, is characterized in that, step 1) gained slurry is accomplished to from preparation the timed interval be added into polyacrylate pressure-sensitive and is no more than 20 minutes.
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| CN106398596A (en) * | 2016-08-31 | 2017-02-15 | 潍坊恒彩数码影像材料有限公司 | Flame-retardant glue |
| CN108504310A (en) * | 2018-05-09 | 2018-09-07 | 佛山市三水日邦化工有限公司 | A kind of fire-resistant hot melt adhesive |
| CN116120856A (en) * | 2023-01-06 | 2023-05-16 | 江苏荣骐光电材料科技有限公司 | Preparation method of halogen-free flame-retardant double-layer lithium battery aluminum shell blue insulation protection adhesive tape |
| CN116554808A (en) * | 2023-07-10 | 2023-08-08 | 山东鲁阳节能材料股份有限公司 | Flexible flame-retardant adhesive for cable fabric and preparation method thereof |
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| CN102518003A (en) * | 2011-12-27 | 2012-06-27 | 四川东材科技集团股份有限公司 | Preparation method for halogen-free flame retardant polyester labeled paper |
| CN102719206A (en) * | 2012-05-31 | 2012-10-10 | 四川东材科技集团股份有限公司 | Preparation method of halogen-free environment-friendly flame-retardant acrylate pressure-sensitive adhesive |
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