CN101153091B - Additive agent for dragging and squeezing glass fiber reinforced plastics product and method of producing the same - Google Patents
Additive agent for dragging and squeezing glass fiber reinforced plastics product and method of producing the same Download PDFInfo
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- CN101153091B CN101153091B CN2007100531034A CN200710053103A CN101153091B CN 101153091 B CN101153091 B CN 101153091B CN 2007100531034 A CN2007100531034 A CN 2007100531034A CN 200710053103 A CN200710053103 A CN 200710053103A CN 101153091 B CN101153091 B CN 101153091B
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Abstract
The present invention relates to an additive for pultruded glass steel products and a preparation method thereof. The additive for pultruded glass steel products is characterized in that the additive is prepared by high-carbon fatty alcohol, phosphorus pentoxide and organic amine used as raw materials. The molar ratio of the high-carbon fatty alcohol, phosphorus pentoxide and organic amine is (1.5 to 3.5) : 1.0 : (0.1 to 0.4). The preparation method of the additive for pultruded glass steel products is characterized in that the method comprises the following steps: the high-carbon fatty alcohol, phosphorus pentoxide and organic amine are weighed for preparation according to the molar ratio of the high-carbon fatty alcohol, phosphorus pentoxide and organic amine of (1.5 to 3.5) : 1.0 : (0.1 to 0.4). At first, the high-carbon fatty alcohol and phosphorus pentoxide do the esterification reaction; then the organic amine is added for neutralization reaction to prepare the additive for pultruded glass steel products. The additive for pultruded glass steel products of the present invention is colorless, transparent, close to neutrality, and has the functions of internal demoulding and fire resistance.
Description
Technical field
The present invention relates to a kind of additive that is used for dragging and squeezing glass fiber reinforced plastics product and preparation method thereof.
Background technology
Pultrusion molding process is a kind of special process in the glass reinforced plastic moulding process, with the continuous tow (glass fibre, carbon fiber etc.) of solvent impregnated resin glue, felt etc., under the effect of tractive force, by mould extrusion molding and curing, the glass fiber reinforced plastics product that continuously production length is not limit, flexible design, moulding is easy.
In the moulding process of product, can produce very strong bounding force between moulding product and the metal die surface, the additional load of on metal die, adhering for the glass fiber reinforced plastics product that prevents moulding, must between goods and metal die, apply releasing agent from mould, to guarantee the excellent of products surface quality and mould so that goods are easy to deviate from.Early stage pultrusion molding process is used external release agent more, and commonly used have silicone oil etc.Be that releasing agent is put into special-purpose groove in the use, when product is pulled, releasing agent is taken to the surface of the glass fibre forming composition that is soaked with resin, entering mould molding then solidifies, reach demoulding effect, but the releasing agent consumption is very big and products surface quality is undesirable, has now used inner pattern releasing agent applicable instead.In the glass reinforced plastic pultrude process, using maximum inner pattern releasing agent applicables is Zinic stearas, still, because resin viscosity is big, directly add powder stearic acid zinc and be difficult to stir, and stearyl ester zinc is loose, volume is big, entrapped air is more, causes the resin steam bubble many, and product surface gloss is relatively poor.So in pultrusion was produced, people more were ready usually to use and are liquid inner pattern releasing agent applicable at normal temperatures, as alkyl phosphate, it has many advantages: (1), be easy to disperse in resin; (2), when reducing the pultrusion resistance, enhance productivity; (3), can reduce the surface tension of resin compound, reduce resin viscosity, improve the wetting property of resin to strongthener, filler, improve resin flow; (4), auxiliary froth breaking and improve the surface quality of parts, make product surface bright and clean; (5), do not influence the curing characteristics of resin, do not change the working life of hybrid resin, do not influence the physical and mechanical property of goods, do not influence the weathering resistance of goods etc.But at present commercially available alkyl phosphate inner pattern releasing agent applicable mostly is a tart, so in use following problem can occur: (1), can cause colour-change when using the pigment of acid labile; (2), when using basic filler, as lime carbonate, acid releasing agent can react with it, causes that the viscosity of compound increases, but can not influence stripping result; (3) if filler is an aluminium hydroxide, acid releasing agent also can be emitted moisture content in the compound solidification process except meeting makes the viscosity increase of compound, cause problems such as bubble, crackle.In addition, commercially available alkyl phosphate inner pattern releasing agent applicable mostly is yellow greatly at present, and this has limited it and can not use in making the flint glass steel work.
Glass fiber reinforced plastics product by the pultrude process moulding has high-strength light, corrosion resistance and good, and electrical insulation capability is good, and characteristics such as transmittance height are widely used in chemical anticorrosion, building, shipbuilding, vehicle, electrician, light industry, daily etc.But because the used synthetic resins of glass reinforced plastic is organic high molecular compound, as unsaturated polyester resin, Resins, epoxy, resol etc., main carbon containing, hydrogen two elements, very easily burning, therefore, the flame retardant resistance of raising glass fiber reinforced plastics product is the current problem that presses for solution.
The environment friendly flame retardant of Halogen, low cigarette, low toxicity is the target that people pursue always, aluminium hydroxide, magnesium hydroxide, antimonous oxide etc. are widely used in the glass reinforced plastic production as the filler and the fire retardant of cheapness, but the amount of need adding is bigger, and the physical and mechanical properties of glass fiber reinforced plastics product is influenced to some extent.The organophosphorus of having developed and being widely used is a non-halogen phosphoric acid ester combustion inhibitor, and as triethyl phosphate, tributyl phosphate, trioctyl phosphate, triphenylphosphate, xylenylphosphate, xylyl diphenyl phosphate etc., flame retardant effect are not good, and its major function is plasticising.Novel phosphorus-nitrogen synergistic system fire retardant as melamine phosphate, is an important directions of current research, and the outstanding advantage of phosphorus-nitrogen flame-retardant system is that addition is few, and flame retardant effect is good, and its gas toxicity that discharges is low.
Summary of the invention
The purpose of this invention is to provide a kind of water white transparency, approaching neutrality, have additive agent for dragging and squeezing glass fiber reinforced plastics product of the interior demoulding and anti-flaming function and preparation method thereof.
To achieve these goals, technical scheme of the present invention is: additive agent for dragging and squeezing glass fiber reinforced plastics product, it is characterized in that it is formed by high-carbon fatty alcohol, Vanadium Pentoxide in FLAKES and organic amine feedstock production, the mol ratio of high-carbon fatty alcohol, Vanadium Pentoxide in FLAKES, organic amine is 1.5-3.5: 1.0: 0.1-0.4.
Described high-carbon fatty alcohol is the mixture of the monohydroxy-alcohol of the monohydroxy-alcohol of C6-C12 scope or C6-C12 scope, as in n-Octanol, nonylcarbinol, the lauryl alcohol etc. any one or any one more than mixture, during any one above mixing, be any proportioning.
Described Vanadium Pentoxide in FLAKES is an analytical pure, and purity is greater than 98wt%.
Described organic amine is aliphatic amides such as triethylamine, diethylamine or trolamine.
The preparation method of above-mentioned additive agent for dragging and squeezing glass fiber reinforced plastics product is characterized in that it comprises the steps:
1) mol ratio by high-carbon fatty alcohol, Vanadium Pentoxide in FLAKES, organic amine is 1.5-3.5: 1.0: 0.1-0.4 takes by weighing high-carbon fatty alcohol, Vanadium Pentoxide in FLAKES, organic amine, and is standby;
2) in the four-hole boiling flask that agitator, prolong, thermometer are housed, add high-carbon fatty alcohol, four-hole boiling flask is put into ice-water bath, and logical nitrogen protection in four-hole boiling flask, starts stirring;
3) when the temperature of four-hole boiling flask is lower than 5 ℃, in four-hole boiling flask, add Vanadium Pentoxide in FLAKES, and powerful the stirring, when being higher than 15 ℃, temperature stops to add Vanadium Pentoxide in FLAKES; When the temperature of four-hole boiling flask is lower than 5 ℃ once more, add Vanadium Pentoxide in FLAKES again, as follows repeatedly, to adding (time of cost is 0.5-1.0 hour) till all Vanadium Pentoxide in FLAKESs;
4) remove the ice-water bath of four-hole boiling flask, continue to be stirred to room temperature, obtain Vanadium Pentoxide in FLAKES homodisperse turbid liquid in high-carbon fatty alcohol, then four-hole boiling flask is put into oil bath, be warming up to 65-75 ℃ and carry out esterification, the transparent liquid that certain viscosity is arranged 0.5 promptly become colorless after hour continues reaction 2.0-3.0 hour;
5) remove the oil bath of four-hole boiling flask, stop heating and continue to be stirred to room temperature, then four-hole boiling flask is put into ice-water bath, be lower than 20 ℃ in temperature, in four-hole boiling flask, drip the liquid organic amine and carry out neutralization reaction, get additive agent for dragging and squeezing glass fiber reinforced plastics product (it is water white near neutral alkyl phosphate amine salt compound).
The present invention has overcome two main drawbacks of the present commercially available alkyl phosphate inner pattern releasing agent applicable that is used for dragging and squeezing glass fiber reinforced plastics product: the one, have color (faint yellow), and the 2nd, acidity is strong (the about 1-3 of pH value) too; The additive agent for dragging and squeezing glass fiber reinforced plastics product of the present invention's preparation, it is water white near neutral alkyl phosphate amine salt compound, has the function of inner pattern releasing agent applicable and fire retardant simultaneously.
Product of the present invention and existing product relatively have following advantage:
1) product water white transparency: be water white liquid under the normal temperature, viscosity is little, can use in making colourless dragging and squeezing glass fiber reinforced plastics product, has enlarged use range.
2) product P H value is high, near neutral, can protect metal die to avoid corrosion, prolongs die life; Simultaneously it reacts hardly with basic filler, so can not make the sizing material retrogradation, and rubber mobility is good.
3) product uses in dragging and squeezing glass fiber reinforced plastics product, not only has the function of inner pattern releasing agent applicable, still is phosphorus-nitrogen synergistic system fire retardant simultaneously, has the function of fire retardant.
Embodiment
In order to understand the present invention better, further illustrate content of the present invention below in conjunction with embodiment, but content of the present invention not only is confined to the following examples.
Embodiment 1:
Additive agent for dragging and squeezing glass fiber reinforced plastics product, it is by high-carbon fatty alcohol (ROH), Vanadium Pentoxide in FLAKES (P
2O
5) and the organic amine feedstock production form, the mol ratio of high-carbon fatty alcohol, Vanadium Pentoxide in FLAKES, organic amine is 2.5: 1.0: 0.3.Described high-carbon fatty alcohol is a n-Octanol; Described Vanadium Pentoxide in FLAKES is an analytical pure, and purity is greater than 98wt% (weight percentage); Described organic amine is a triethylamine.
The preparation method of above-mentioned additive agent for dragging and squeezing glass fiber reinforced plastics product, it comprises the steps:
1) be to take by weighing high-carbon fatty alcohol, Vanadium Pentoxide in FLAKES, organic amine at 2.5: 1.0: 0.3 by the mol ratio of high-carbon fatty alcohol, Vanadium Pentoxide in FLAKES, organic amine, standby; Described high-carbon fatty alcohol is a n-Octanol; Described organic amine is a triethylamine;
2) in the four-hole boiling flask that agitator, prolong, thermometer are housed, add high-carbon fatty alcohol, four-hole boiling flask is put into ice-water bath, and logical nitrogen protection in four-hole boiling flask, starts stirring;
3) when the temperature of four-hole boiling flask is lower than 5 ℃, in four-hole boiling flask, add Vanadium Pentoxide in FLAKES, and powerful the stirring, when being higher than 15 ℃, temperature stops to add Vanadium Pentoxide in FLAKES; When the temperature of four-hole boiling flask is lower than 5 ℃ once more, add Vanadium Pentoxide in FLAKES again, as follows repeatedly, to adding (time of cost is 0.5-1.0 hour) till all Vanadium Pentoxide in FLAKESs;
4) remove the ice-water bath of four-hole boiling flask, continue to be stirred to room temperature, obtain Vanadium Pentoxide in FLAKES homodisperse turbid liquid in high-carbon fatty alcohol, then four-hole boiling flask is put into oil bath, be warming up to 70 ℃ and carry out esterification, the transparent liquid that certain viscosity is arranged 0.5 promptly become colorless after hour continues reaction 2.0-3.0 hour;
5) remove the oil bath of four-hole boiling flask, stop heating and continue to be stirred to room temperature, then four-hole boiling flask is put into ice-water bath, be lower than 20 ℃ in temperature, in four-hole boiling flask, drip the liquid organic amine and carry out neutralization reaction, the neutralization reaction time is 2.0-3.0 hour, gets additive agent for dragging and squeezing glass fiber reinforced plastics product (it is water white near neutral alkyl phosphate amine salt compound).
The basic physicals test result such as the table 1 of additive agent for dragging and squeezing glass fiber reinforced plastics product.
Embodiment 2:
The preparation method is with embodiment 1, n-Octanol be replaced by the monohydroxy-alcohol mixture that contains the C8-C12 scope (as the mixture of nonylcarbinol and lauryl alcohol, the mole number of nonylcarbinol, lauryl alcohol respectively account for high-carbon fatty alcohol 1/2).The basic physicals test result such as the table 1 of additive agent for dragging and squeezing glass fiber reinforced plastics product.
Embodiment 3:
The preparation method is replaced by trolamine to triethylamine with embodiment 1.The basic physicals test result such as the table 1 of additive agent for dragging and squeezing glass fiber reinforced plastics product.
Embodiment 4:
The preparation method is with embodiment 3, n-Octanol be replaced by the monohydroxy-alcohol mixture that contains the C8-C12 scope (as the mixture of nonylcarbinol and lauryl alcohol, the mole number of nonylcarbinol, lauryl alcohol respectively account for high-carbon fatty alcohol 1/2).The basic physicals test result such as the table 1 of additive agent for dragging and squeezing glass fiber reinforced plastics product.
Table 1, basic physicals test result
Application in dragging and squeezing glass fiber reinforced plastics product:
Application example 1:
The glue prescription of pulling and extruding glass fiber section bar is: 100 parts of unsaturated polyester resins for general purposes (weight), 2 parts of methylethyl ketone peroxides (weight), 3 parts of naphthoic acid cobalt solution (weight), 20 parts in lime carbonate (weight), the additive agent for dragging and squeezing glass fiber reinforced plastics product (alkyl phosphate amine salt compound) 2 parts (weight) of embodiment 1 preparation; Strongthener adopts woven glass roving fabric: 2600Tex (the gram number of every km), and the weight fraction in pulling and extruding glass fiber section bar is 75%; Pultrusion speed is 30-40cm/min; Mould three districts temperature setting: 100 ℃ in I district, 120 ℃ in II district, 130 ℃ in III district.Basic physicals test result of its section bar such as table 2.
Application example 2:
The preparation method does not only add the additive agent for dragging and squeezing glass fiber reinforced plastics product (alkyl phosphate amine salt compound) of embodiment 1 preparation with application example 1.Basic physicals test result of its section bar such as table 2.
Application example 3:
The preparation method is replaced by Zinic stearas to the additive agent for dragging and squeezing glass fiber reinforced plastics product (alkyl phosphate amine salt compound) of embodiment 1 preparation with application example 1.Basic physicals test result of its section bar such as table 2.
Table 2, the basic physicals test result of pulling and extruding glass fiber section bar
Embodiment 5:
Additive agent for dragging and squeezing glass fiber reinforced plastics product, it is formed by high-carbon fatty alcohol, Vanadium Pentoxide in FLAKES and organic amine feedstock production, and the mol ratio of high-carbon fatty alcohol, Vanadium Pentoxide in FLAKES, organic amine is 1.5: 1.0: 0.1.
Described high-carbon fatty alcohol is a nonylcarbinol; Described Vanadium Pentoxide in FLAKES is an analytical pure, and purity is greater than 98wt%; Described organic amine is a diethylamine.
The preparation method of above-mentioned additive agent for dragging and squeezing glass fiber reinforced plastics product, it comprises the steps:
1) be to take by weighing high-carbon fatty alcohol, Vanadium Pentoxide in FLAKES, organic amine at 1.5: 1.0: 0.1 by the mol ratio of high-carbon fatty alcohol, Vanadium Pentoxide in FLAKES, organic amine, standby; Described high-carbon fatty alcohol is a nonylcarbinol; Described Vanadium Pentoxide in FLAKES is an analytical pure, and purity is greater than 98wt%; Described organic amine is a diethylamine;
2) in the four-hole boiling flask that agitator, prolong, thermometer are housed, add high-carbon fatty alcohol, four-hole boiling flask is put into ice-water bath, and logical nitrogen protection in four-hole boiling flask, starts stirring;
3) when the temperature of four-hole boiling flask is lower than 5 ℃, in four-hole boiling flask, add Vanadium Pentoxide in FLAKES, and powerful the stirring, when being higher than 15 ℃, temperature stops to add Vanadium Pentoxide in FLAKES; When the temperature of four-hole boiling flask is lower than 5 ℃ once more, add Vanadium Pentoxide in FLAKES again, as follows repeatedly, to adding (time of cost is 0.5-1.0 hour) till all Vanadium Pentoxide in FLAKESs;
4) remove the ice-water bath of four-hole boiling flask, continue to be stirred to room temperature, obtain Vanadium Pentoxide in FLAKES homodisperse turbid liquid in high-carbon fatty alcohol, then four-hole boiling flask is put into oil bath, be warming up to 65 ℃ and carry out esterification, the transparent liquid that certain viscosity is arranged 0.5 promptly become colorless after hour continues reaction 2.0-3.0 hour;
5) remove the oil bath of four-hole boiling flask, stop heating and continue to be stirred to room temperature, then four-hole boiling flask is put into ice-water bath, be lower than 20 ℃ in temperature, in four-hole boiling flask, drip the liquid organic amine and carry out neutralization reaction, the neutralization reaction time is 2.0-3.0 hour, gets additive agent for dragging and squeezing glass fiber reinforced plastics product (it is water white near neutral alkyl phosphate amine salt compound).
Embodiment 6:
Additive agent for dragging and squeezing glass fiber reinforced plastics product, it is formed by high-carbon fatty alcohol, Vanadium Pentoxide in FLAKES and organic amine feedstock production, and the mol ratio of high-carbon fatty alcohol, Vanadium Pentoxide in FLAKES, organic amine is 3.5: 1.0: 0.4.
Described high-carbon fatty alcohol is the mixture of n-Octanol, nonylcarbinol and lauryl alcohol, and the mole number of n-Octanol, nonylcarbinol, lauryl alcohol respectively accounts for 1/3 of high-carbon fatty alcohol; Described Vanadium Pentoxide in FLAKES is an analytical pure, and purity is greater than 98wt%; Described organic amine is a trolamine;
The preparation method of above-mentioned additive agent for dragging and squeezing glass fiber reinforced plastics product, it comprises the steps:
1) mol ratio by high-carbon fatty alcohol, Vanadium Pentoxide in FLAKES, organic amine is 1.5-3.5: 1.0: 0.1-0.4 takes by weighing high-carbon fatty alcohol, Vanadium Pentoxide in FLAKES, organic amine, and is standby; Described high-carbon fatty alcohol is the mixture of n-Octanol, nonylcarbinol and lauryl alcohol, and the mole number of n-Octanol, nonylcarbinol, lauryl alcohol respectively accounts for 1/3 of high-carbon fatty alcohol; Described Vanadium Pentoxide in FLAKES is an analytical pure, and purity is greater than 98wt%; Described organic amine is a trolamine;
2) in the four-hole boiling flask that agitator, prolong, thermometer are housed, add high-carbon fatty alcohol, four-hole boiling flask is put into ice-water bath, and logical nitrogen protection in four-hole boiling flask, starts stirring;
3) when the temperature of four-hole boiling flask is lower than 5 ℃, in four-hole boiling flask, add Vanadium Pentoxide in FLAKES, and powerful the stirring, when being higher than 15 ℃, temperature stops to add Vanadium Pentoxide in FLAKES; When the temperature of four-hole boiling flask is lower than 5 ℃ once more, add Vanadium Pentoxide in FLAKES again, as follows repeatedly, to adding (time of cost is 0.5-1.0 hour) till all Vanadium Pentoxide in FLAKESs;
4) remove the ice-water bath of four-hole boiling flask, continue to be stirred to room temperature, obtain Vanadium Pentoxide in FLAKES homodisperse turbid liquid in high-carbon fatty alcohol, then four-hole boiling flask is put into oil bath, be warming up to 75 ℃ and carry out esterification, the transparent liquid that certain viscosity is arranged 0.5 promptly become colorless after hour continues reaction 2.0-3.0 hour;
5) remove the oil bath of four-hole boiling flask, stop heating and continue to be stirred to room temperature, then four-hole boiling flask is put into ice-water bath, be lower than 20 ℃ in temperature, in four-hole boiling flask, drip the liquid organic amine and carry out neutralization reaction, the neutralization reaction time is 2.0-3.0 hour, gets additive agent for dragging and squeezing glass fiber reinforced plastics product (it is water white near neutral alkyl phosphate amine salt compound).
Claims (4)
1. additive agent for dragging and squeezing glass fiber reinforced plastics product is characterized in that it is formed by high-carbon fatty alcohol, Vanadium Pentoxide in FLAKES and organic amine feedstock production, and the mol ratio of high-carbon fatty alcohol, Vanadium Pentoxide in FLAKES, organic amine is 1.5-3.5: 1.0: 0.1-0.4;
Described high-carbon fatty alcohol is the mixture of the monohydroxy-alcohol of the monohydroxy-alcohol of C6-C12 scope or C6-C12 scope; Described organic amine is triethylamine, diethylamine or trolamine.
2. additive agent for dragging and squeezing glass fiber reinforced plastics product according to claim 1 is characterized in that: the monohydroxy-alcohol of C6-C12 scope is n-Octanol, nonylcarbinol or lauryl alcohol.
3. additive agent for dragging and squeezing glass fiber reinforced plastics product according to claim 1 is characterized in that: described Vanadium Pentoxide in FLAKES is an analytical pure, and purity is greater than 98wt%.
4. the preparation method of additive agent for dragging and squeezing glass fiber reinforced plastics product as claimed in claim 1 is characterized in that it comprises the steps:
1) mol ratio by high-carbon fatty alcohol, Vanadium Pentoxide in FLAKES, organic amine is 1.5-3.5: 1.0: 0.1-0.4 takes by weighing high-carbon fatty alcohol, Vanadium Pentoxide in FLAKES, organic amine, and is standby;
Described high-carbon fatty alcohol is the mixture of the monohydroxy-alcohol of the monohydroxy-alcohol of C6-C12 scope or C6-C12 scope; Described organic amine is triethylamine, diethylamine or trolamine;
2) in the four-hole boiling flask that agitator, prolong, thermometer are housed, add high-carbon fatty alcohol, four-hole boiling flask is put into ice-water bath, and logical nitrogen protection in four-hole boiling flask, starts stirring;
3) when the temperature of four-hole boiling flask is lower than 5 ℃, in four-hole boiling flask, add Vanadium Pentoxide in FLAKES, and powerful the stirring, when being higher than 15 ℃, temperature stops to add Vanadium Pentoxide in FLAKES; When the temperature of four-hole boiling flask is lower than 5 ℃ once more, add Vanadium Pentoxide in FLAKES again, as follows repeatedly, till adding all Vanadium Pentoxide in FLAKESs;
4) remove the ice-water bath of four-hole boiling flask, continue to be stirred to room temperature, obtain Vanadium Pentoxide in FLAKES homodisperse turbid liquid in high-carbon fatty alcohol, then four-hole boiling flask is put into oil bath, be warming up to 65-75 ℃ and carry out esterification, the transparent liquid that certain viscosity is arranged 0.5 promptly become colorless after hour continues reaction 2.0-3.0 hour;
5) remove the oil bath of four-hole boiling flask, stop heating and continue to be stirred to room temperature, then four-hole boiling flask is put into ice-water bath, be lower than 20 ℃, in four-hole boiling flask, drip the liquid organic amine and carry out neutralization reaction in temperature, must additive agent for dragging and squeezing glass fiber reinforced plastics product.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2007100531034A CN101153091B (en) | 2007-08-31 | 2007-08-31 | Additive agent for dragging and squeezing glass fiber reinforced plastics product and method of producing the same |
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| CN2007100531034A CN101153091B (en) | 2007-08-31 | 2007-08-31 | Additive agent for dragging and squeezing glass fiber reinforced plastics product and method of producing the same |
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| CN101153091B true CN101153091B (en) | 2010-04-14 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1335352A (en) * | 2000-07-22 | 2002-02-13 | 中国科学技术大学 | Nitrogenous phosphide fire retardant without halide and capable of being radiation cured and its producing process |
| CN1335332A (en) * | 2001-08-28 | 2002-02-13 | 巴陵石化岳阳石油化工总厂 | Halogen-free intumescent flame retardant composition for polyolefin |
| CN1733874A (en) * | 2004-08-13 | 2006-02-15 | 抚顺市雷特化工科技有限公司 | Oil additive preparation method |
| CN1816585A (en) * | 2003-05-09 | 2006-08-09 | 普罗米修斯发展有限公司 | A method of producing polymeric material |
| CN1830986A (en) * | 2006-04-11 | 2006-09-13 | 四川师范大学 | Method for preparing ammonium salts of cyclohexanpentol phosphate ester |
-
2007
- 2007-08-31 CN CN2007100531034A patent/CN101153091B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1335352A (en) * | 2000-07-22 | 2002-02-13 | 中国科学技术大学 | Nitrogenous phosphide fire retardant without halide and capable of being radiation cured and its producing process |
| CN1335332A (en) * | 2001-08-28 | 2002-02-13 | 巴陵石化岳阳石油化工总厂 | Halogen-free intumescent flame retardant composition for polyolefin |
| CN1816585A (en) * | 2003-05-09 | 2006-08-09 | 普罗米修斯发展有限公司 | A method of producing polymeric material |
| CN1733874A (en) * | 2004-08-13 | 2006-02-15 | 抚顺市雷特化工科技有限公司 | Oil additive preparation method |
| CN1830986A (en) * | 2006-04-11 | 2006-09-13 | 四川师范大学 | Method for preparing ammonium salts of cyclohexanpentol phosphate ester |
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