Refractory drips non-halogen polymer-type additive with fire-retardant and its production and use
One, technical field
The invention belongs to refractory and drip the technical field that additive and fire retardant and preparation method thereof reach purposes, specifically, it is remarkable especially that the present invention is that a kind of refractory drips effect, also has fire retardation simultaneously, the alternative existing additive flame retardant that is used for polyester etc., the preparation method of the especially non-halogen polymer-type additive of Halogen additive flame retardant, and this additive and its are used for polyester and the polyamide polymers refractory drips and fire-retardant purposes.
Two, background technology
Existing most polymers, as polyester, polymeric amide etc., do not possess flame retardant resistance, but expansion along with its Application Areas, in some special use occasion, finishing material or the used aspects such as protective clothing of special industry as aviation, public place of entertainment, family etc., then require it to reach certain fire-retardant requirement, otherwise will improve the insecurity of fire greatly.Moreover, these polymkeric substance also can drip under burning or high temperature in fusion, thereby have limited them and taken the fiber use in the use, particularly conduct of some occasion.Because when running into fire, the polymer melt drippage not only can make the people scald, and also may cause new fire because of other material that ignites behind the molten drop drippage.
In order to make high molecular polymer possess non-flame properties, it carry out fire-retardantization with regard to needing.At present macromolecular material is carried out fire-retardantization two kinds of methods are roughly arranged: the one, copolymerization is flame-retardant modified, is about to fire-retardant monomer with the polymer monomer copolymerization.The 2nd, add the fire retardant modification.But adopt the sort of mode carry out fire-retardantization no matter be, the research emphasis of prior art all is the fire-retardant aspect that is placed on polymkeric substance, and pay close attention to very few to the dripping property of refractory of polymkeric substance, this makes the great majority all very high flame-retardant polymer of limiting oxygen index determination method evaluation, its dripping property of refractory is all very poor, as the clear 47-32299 of Japanese Patent disclosed " fire-retardantization polyester synthetics ", German patent DE-OS 2438967, DE-OS 2253207, the disclosed respectively flame retardant polyester setting composition that contains the macromolecule organic phosphine compound of DE-OS 213235, contain the flame retardant thermoplastic polyester resin of diaryl-phosphide and the fire-retardant poly terephthalic acid propane of phosphorated ester additive etc., all can not satisfy simultaneously refractory is dripped and fire-retardant service requirements.
Three, summary of the invention
The objective of the invention is defective, provide a kind of refractory to drip and fire-retardant non-halogen polymer-type additive at the prior art existence.Another object of the present invention provides the preparation refractory and drips method with fire-retardant non-halogen polymer-type additive.Last purpose of the present invention provides the purposes of this additive.
Refractory provided by the invention drips and fire-retardant non-halogen polymer-type additive, and the feature that is showed is to have following repeated structural unit:
Wherein Z is the divalent aromatic base; R is an aryl; Polymerization degree n 〉=1, preferred degree of polymerization n is 4~30.And the divalent aromatic base then is in the diphenols compound of following structure any before polyreaction:
Wherein X is straight or branched alkyl, sulfuryl, azo-group or the sulphur atom of carbonatoms 1~6; Aryl is phenyl, naphthyl, monoalkyl substituted-phenyl or monoalkyl substituted naphthyl.
The above-mentioned refractory of preparation provided by the invention drips the method with fire-retardant non-halogen polymer-type additive, and this method is that any that adopt diphenols compound with following structure carries out melt polycondensation reaction as raw material (I) and raw material (II):
Wherein X is straight or branched alkyl, sulfuryl, azo-group or the sulphur atom of carbonatoms 1~6, it is characterized in that raw material (II) is the compound with following general formula:
Y is a halogen atom in the general formula, preferred chlorine atom; R is an aryl, and the processing step of its preparation and condition are earlier raw material (I), raw material (II) to be added in the reaction vessel, feed nitrogen then, and under agitation be warming up to raw materials melt, reacted 2~10 hours, or earlier raw material (I) is added in the reactor, feed nitrogen then, and under agitation be warming up to fusion, drip raw material (II) again, 0.5~2 hour dropping time is after being added dropwise to complete, reacted 2~10 hours, the gained reactant promptly can be used as product and directly uses.Use after also reactant can being purified, promptly after the reactant cooling, adding solvent to reactant dissolves fully, pour volume then into and be in 5 times of reactant solution volumes and the above coprecipitator, precipitation separate out the pure white powdery product and from coprecipitator suction filtration go out the white powder product, dry then getting final product.
The general formula raw material (I) that is adopted in refractory provided by the invention drips preparation method with fire-retardant polymer-type additive is 0.9~1.1: 1 with the mole proportioning of raw material (II).
In order to accelerate polycondensation speed, also can when polycondensation, add catalyzer, the mole proportioning of catalyzer and raw material (II) is 0.001~0.1: 1, specifically can select calcium chloride or aluminum chloride or zinc chloride in the Lewis acid for use; Solvent that is adopted during purification and coprecipitator should be selected for use according to the solvability and insoluble the exploration respectively of product of the concrete product of melt phase polycondensation, the inventor is through exploring, can select chloroform or phenylcarbinol for use to solvent among the embodiment that provides later, coprecipitator can be selected methyl alcohol, dehydrated alcohol or anhydrous diethyl ether for use.
The purposes of dripping with fire-retardant polymer-type additive with the refractory of method for preparing is to be used for polycondensation method synthetic polymkeric substance, drips with fire-retardant as the refractory of polyester and polyamide polymers.
The present invention has the following advantages:
1. because additive provided by the invention is to be formed by the sulfo-phosphono dihalo-that contains aryl and diphenols compound polymerization, wherein contain the two keys of phosphorus sulphur, so its one-tenth charcoal is good, with polymeric substrate, especially polyester (fiber) blend after, do not have the molten drop generation substantially.
2. because additive provided by the invention is a polymer-type, thereby Heat stability is good, good with the polymeric substrate consistency of blend, trevira especially, and be difficult for oozing out from fiber surface, can guarantee the weather resistance that material is fire-retardant.
3. because additive provided by the invention is not halogen-containing, help environmental protection, so it has a good application prospect.
4. preparation method of the present invention is simple, and technical maturity is easy to control.
5. additive provided by the invention can be used for polycondensation method synthetic polymkeric substance, drips with fire-retardant as the refractory of polyester and polyamide polymers.
Four, embodiment
Embodiment given below is that the invention will be further described, but can not be interpreted as limiting the scope of the invention, and this area professional can make some nonessential improvement and adjustment to the present invention according to above content of the present invention.
Embodiment 1:
Present embodiment is the preparation of poly-thio phenyl phosphonic acids biconjugate hydroxy phenyl sulfone ester, and its reaction formula is:
Whipping appts being housed and the calcium chloride that adds 1mol thio phenyl phosphonyl dichloride, 1mol bisphenol S and 0.08mol more than 500 milliliters in the neck bottle of import and export of nitrogen being arranged, feed nitrogen then and under agitation heat to 250 ℃ gradually, made it frit reaction 3 hours; After question response finishes cooling, adding chloroform to reactant dissolves fully, pour volume then into and be in 5 times of reactant solution volumes and the above methyl alcohol and precipitate, separate out the white powder product, white powder product suction filtration from coprecipitator methyl alcohol is gone out, and dry then, drying can be taked natural air drying, also can take oven dry, preferably vacuum drying.Present embodiment productive rate 99%, 180 ℃ of product melt temperatures.
Embodiment 2:
Present embodiment is the preparation of poly-thio phenyl phosphonic acids 2.2-biconjugate hydroxy phenyl propane ester, and its reaction formula is:
Put into 1mol thio phenyl phosphonyl dichloride more than 500 milliliters in the neck bottle what whipping appts is housed and import and export of nitrogen arranged, the calcium chloride of 1mol dihydroxyphenyl propane and 0.05mol, feed nitrogen then and under agitation heat to 200 ℃ gradually, make it frit reaction 5 hours, and improved temperature to 250 ℃ reaction 3 hours again; After question response finishes cooling, add phenylcarbinol to reactant and dissolve fully, pour volume then into and be in 5 times of reactant solution volumes and the above dehydrated alcohol and precipitate, separate out the white powder product; White powder product suction filtration from the coprecipitator dehydrated alcohol is gone out, and oven dry gets final product then.Productive rate 90%, 140 ℃ of product melt temperatures.
Embodiment 3:
Present embodiment is the preparation of poly-thio phenyl phosphonic acids biconjugate hydroxy phenyl sulfone ester, and its reaction formula is:
Whipping appts is being housed and more than 500 milliliters in the neck bottle of import and export of nitrogen are being arranged, the aluminum chloride that adds 0.5mol bisphenol S and 0.03mol earlier, feed nitrogen then and under agitation be warming up to 230 ℃ gradually, make it fusion, drip 0.55mol thio phenyl phosphonyl dichloride again, the 1 hour dropping time of control, after being added dropwise to complete, reacted 3 hours; After question response finishes cooling, add chloroform to reactant and dissolve fully, pour volume then into and be in 5 times of reactant solution volumes and the above methyl alcohol and precipitate, separate out the white powder product; White powder product suction filtration from coprecipitator methyl alcohol is gone out, and oven dry gets final product then.Productive rate 95%, 180 ℃ of product melt temperatures.
Embodiment 4:
Present embodiment is the preparation of poly-thio phenyl phosphonic acids 2.2-biconjugate hydroxy phenyl propane ester, and its reaction formula is:
Whipping appts is being housed and more than 500 milliliters in the neck bottle of import and export of nitrogen are being arranged, the zinc chloride that adds 0.6mol dihydroxyphenyl propane and 0.04mol earlier, feed nitrogen then and under agitation be warming up to 200 ℃ gradually, make it fusion, drip 0.01mol thio phenyl phosphonyl dichloride again, the 1.5 hours dropping time of control, be added dropwise to complete back reaction earlier 3 hours, and then be warming up to 250 ℃, reacted 5 hours; After question response finishes cooling, add phenylcarbinol to reactant and dissolve fully, pour volume then into and be in 5 times of reactant solution volumes and the above anhydrous diethyl ether and precipitate, separate out the white powder product; White powder product suction filtration from the coprecipitator anhydrous diethyl ether is gone out, and oven dry gets final product then.Productive rate 85%, 140 ℃ of product melt temperatures.
Drip and flame retardant properties in order to investigate the refractory that refractory provided by the invention drips with fire-retardant non-halogen polymer-type additive, the present invention has measured its dripping property of refractory by the GB4609-84 specified standards, and adopted JF-3 type oxygen index instrument by the GB2406-80 specified standards, molten the mixing of itself and polyester made 130 * 13 * 3 millimeters standard batten and the standard batten of pure polyester carries out test comparison, result such as following table.
Description of materials | The molten drop behavior | Oxygen index (%) |
Pure PET | Molten drop | ????21 |
????PET/TPSPP | Molten drop not | ????29.5 |
Annotate: PET is a polyester; TPSPP is poly-thio phenyl phosphonic acids biconjugate hydroxy phenyl sulfone ester.