CN1257219C - Halogen less expansion type polyolefine incombustible agent and its preparation method - Google Patents
Halogen less expansion type polyolefine incombustible agent and its preparation method Download PDFInfo
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- CN1257219C CN1257219C CN 200310122097 CN200310122097A CN1257219C CN 1257219 C CN1257219 C CN 1257219C CN 200310122097 CN200310122097 CN 200310122097 CN 200310122097 A CN200310122097 A CN 200310122097A CN 1257219 C CN1257219 C CN 1257219C
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Abstract
The present invention relates to a non-halogen expansion type polyolefine incombustible agent and a preparation method thereof. The incombustible agent comprises (by wt%): 40 to 95% of glycidol amine epoxy resin coating ammonium polyphosphate, 1 to 40% of inorganic matter and 0 to 40% of triazine compound or derivative thereof. The preparation method comprises the technological steps of the preparation of the glycidol amine epoxy resin coating ammonium polyphosphate, the preparation of the polyolefine incombustible agent, etc. Compared with the prior art, the incombustible agent endows a polymer with certain incombustible performance and can not influence the mechanical performance of the polymer.
Description
Technical field
The present invention relates to difficulty (resistance) combustion agent and preparation method thereof, relate in particular to a kind of halogen-free expansible polyolefine incombustible agent and preparation method thereof.
Background technology
In the past, in order to improve thermoplastic resin, particularly the flame retardancy of polyolefin resin is generally used the Halogen incombustible agent always.But the thermoplastic resin of Halogen incombustible agent can produce macro-corrosion, toxic gas and black smoke, seriously contaminate environment when fire and burning disposal.Develop environment-friendly type incombustible agent or difficult combustion system is that incombustible agent has become the task of top priority to replace halogen for this reason.Each state all carries out energetically to the research and development of resin with non-halogen incombustible agent at present.Wherein, phosphorus flame retardant-especially is that the fire-retardant composition of principal constituent is widely studied with ammonium polyphosphate (being called for short APP).
As US4,198,498 have proposed APP and THEIC, melamine, tetramethylolmethane are used together, as polyolefinic foaminess flame-retardant mixture.EP258,685 have introduced APP and THEIC have been mixed method as polyolefin polymer or multipolymer.JP96/12805 has proposed the polyolefine incombustible agent with APP and expanded graphite composition.JP93/39394 has introduced the flame-retarded resin constituent of being made up of polypropylene, APP, tetramethylolmethane and organic silicone compound.JP96/67769 has also reported the flame-retarded resin constituent of being made up of polypropylene, melamine coating APP and dipentaerythritol.JP2002-60385 has also reported the flame-retarded resin constituent of being made up of the reactant of polypropylene, APP, TDI and THEIC.
Though these technology have good difficulty combustion effect, also have various shortcomings, as: the incombustible agent addition is big, causes flame-retarded resin mechanical property variation; Fire retardant has very high water-soluble, causes the rosin products that contains fire retardant when contacting with water, and the loss of fire retardant causes the very fast decline of its flame retardant effect; And the fire retardant that adds graphite is difficult for hiding look; The reactant of TDI and THEIC easily makes fabricated product yellowing etc.
Summary of the invention
Purpose of the present invention is exactly to provide a kind of when giving the certain flame retardancy of polymkeric substance in order to overcome the defective that above-mentioned prior art exists, halogen-free expansible polyolefine incombustible agent that can the impact polymer mechanical property and preparation method thereof.
Purpose of the present invention can be achieved through the following technical solutions:
A kind of halogen-free expansible polyolefine incombustible agent is characterized in that, this incombustible agent comprises following component and content (weight %):
(1) Racemic glycidol amine epoxy resin coated ammonium polyphosphate 40～95%,
(2) inorganics 1～40%,
(3) the triaizine compounds or derivatives thereof 0～40%.
Described Racemic glycidol amine epoxy resin is selected from one or both in tricyanic epoxy resin, the aniline Resins, epoxy.
The molecular formula of described ammonium polyphosphate is (NH
4PO
3)
n, n=50 in the formula～1000.
Described inorganics is selected from one or more in talcum powder, carclazyte, wollastonite, zeolite, silico-aluminate, molecular sieve, kaolin, zircon sand, polynite, mica, wilkinite, lime carbonate, calcium sulfate, silicon-dioxide, calcium oxide, boron trioxide, ammonium borate, ammonium silicate, Calucium Silicate powder, titanium dioxide, antimonous oxide, magnesium oxide, aluminum oxide, aluminium hydroxide, brucite, magnesium hydroxide, the basic carbonate calcium.
Described inorganics can adopt coupling agent and/or tensio-active agent that it is carried out surface treatment.
Described coupling agent and/or tensio-active agent are selected from one or more in silane coupling agent, titanate coupling agent, aluminate coupling agent, nonionogenic tenside, cats product, the fluorochemical surfactant.
Described triaizine compounds or derivatives thereof is selected from the compound that contains triazine ring in the molecule, comprises in melamine, tri methylol melamine, melamine cyanurate, melamine phosphate, bis phosphoric acid tetramethylolmethane melamine salt, guanamine, phenylpropyl alcohol guanamine, methyl guanamines, succinyl-guanamines, the acid of cyanogen urea, trishydroxymethyl cyanurate and derivative, trihydroxyethyl cyanurate and derivative thereof, three-glycidyl isocyanuric acid ester and the derivative thereof one or more.
A kind of preparation method of halogen-free expansible polyolefine incombustible agent is characterized in that, this method comprises following processing step:
(1) preparation of Racemic glycidol amine epoxy resin coated ammonium polyphosphate
(a) at first in the reactor that has heated and stirred, reflux condensate device, add Resins, epoxy and organic solvent or water, heating makes the Resins, epoxy dissolving, adds the ammonium polyphosphate back that stirs then and adds solidifying agent; Perhaps the ammonium polyphosphate powder suspension in organic solvent or water, add Resins, epoxy and the solidifying agent that has been dissolved in the organic solvent simultaneously or successively, wherein the covering amount of Resins, epoxy is 0.5～25 weight % of ammonium polyphosphate;
(b) insulation reaction postcooling, filtration, washing, drying obtain the Resins, epoxy coated ammonium polyphosphate, and the reaction times is 0.5～2 hour;
(2) preparation of polyolefine incombustible agent
Ammonium polyphosphate 40～95 weight % and inorganics 1～40 weight % and triaizine compounds or derivatives thereof 0～40 weight % thorough mixing in mixing machine that the Racemic glycidol amine epoxy resin that step (1) is obtained coats make a kind of halogen-free expansible polyolefine incombustible agent.
Described organic solvent is selected from one or more among methyl alcohol, ethanol, Virahol, acetone, tetrahydrofuran (THF), the DMF.
Described solidifying agent is selected from one or more in amine curing agent, acid anhydride type curing agent and the high score subclass solidifying agent.
If we find that composite again other incombustible agent component makes an addition in the polyolefine with the APP of Racemic glycidol amine epoxy resin coating, then the flame retardancy of polymkeric substance and water tolerance all can satisfy demand of the present invention.The present invention adopts above incombustible agent constituent just, be applied in the polyolefine superpolymer, under the mechanical mechanics property and electrical property situation of not obvious impact polymer, not only give polymkeric substance certain flame retardancy, also improved the forming process temperature of polymkeric substance, and non-hygroscopic through the polymer surfaces of difficulty combustion processing.
Embodiment
Incombustible agent composition (1) among the present invention is the APP that the Racemic glycidol amine epoxy resin coats, and its consumption accounts for 40～95% of fire retardant total amount.The APP molecular formula is (NH
4PO
3)
n, n=50 in the formula～1000, more preferably 〉=500, the APP that the white free-running property powder that water solubility is low, this APP also can be crossed with formaldehyde melamine resin or other resin-coated.Wherein the covering amount of Resins, epoxy is 0.5～25 (wt) % of APP, is preferably 5～20 (wt) % of APP.Such Resins, epoxy such as tricyanic epoxy resin or aniline Resins, epoxy can add Resins, epoxy and organic solvent or water when coating APP, after heating makes the Resins, epoxy dissolving, add then and add solidifying agent again after APP stirs, perhaps the APP powder suspension in organic solvent or water, add Resins, epoxy and the solidifying agent that has been dissolved in the organic solvent simultaneously or successively.Can select following any one or a few epoxy curing agent to be hardened during epoxy resin cure.As amine curing agent: quadrol, diethylene diamine, triethylamine, diethylenetriamine, Triethylenetetramine (TETA), trimethylhexamethylenediamine, isophorone diamine, mphenylenediamine, 4,4 '-diaminodiphenylmethane, 4,4 '-diaminodiphenylsulfone(DDS), Dyhard RU 100 and acid anhydride type curing agent: Tetra hydro Phthalic anhydride, tetrahydrochysene phthalate anhydride, hexahydrophthalic acid anhydride etc. and high score subclass solidifying agent such as low molecular polyamides etc.What effect was made us comparatively satisfaction in the above-mentioned solidifying agent is diethylene diamine, triethylamine, diethylenetriamine.When Resins, epoxy coats APP can with or without organic solvent, organic solvent applicatory is: methyl alcohol, ethanol, Virahol, acetone, tetrahydrofuran (THF), DMF etc.
Incombustible agent composition (2) among the present invention is an inorganics.Specifically enumerate as talcum powder, carclazyte, wollastonite, zeolite, silico-aluminate, molecular sieve, kaolin, zircon sand, polynite, mica, wilkinite, lime carbonate, calcium sulfate, silicon-dioxide, calcium oxide, boron trioxide, amine borate, silicic acid amine, Calucium Silicate powder, titanium dioxide, antimonous oxide, magnesium oxide, aluminum oxide, zircon sand, aluminium hydroxide, brucite, magnesium hydroxide, basic carbonate calcium etc.For promoting the consistency of above-mentioned inorganics and superpolymer, the most handy various coupling agents as: silane coupling agent, titanate coupling agent, aluminate coupling agent etc. and/or tensio-active agent such as nonionogenic tenside, cats product and fluorochemical surfactant etc. carry out surface treatment to it.In the above-mentioned inorganics effect gratifying be silicon-dioxide, calcium oxide, magnesium oxide, zeolite, wollastonite, silico-aluminate, molecular sieve, kaolin, zircon sand, talcum powder, titanium dioxide, antimonous oxide.They can distinguish use separately or two or more mixes use.Its consumption accounts for 1～40 (wt) % of fire retardant total amount, more preferably 5～30 (wt) %.
Incombustible agent composition (3) among the present invention is triaizine compounds and derivative thereof.As: melamine derivatives such as melamine, tri methylol melamine, melamine cyanurate, melamine phosphate, bis phosphoric acid tetramethylolmethane melamine salt; The derivative of guanamines such as guanamine, phenylpropyl alcohol guanamine, methyl guanamines, succinyl-guanamines; The acid of cyanogen urea, trishydroxymethyl cyanurate and derivative thereof, trihydroxyethyl cyanurate and derivative thereof, three-glycidyl isocyanuric acid ester and derivative thereof, cyanogen urea diamide etc.Wherein effect make us comparatively satisfied be trihydroxyethyl cyanurate etc. derivative as: trihydroxyethyl cyanurate and with the reactant of isocyanic ester such as TDI, MDI, HDI or trihydroxyethyl cyanurate and aromatic carboxylic acid as the reactant of terephthalic acid, maleic anhydride etc. or melamine, melamine cyanurate.Above-mentioned triaizine compounds and derivative thereof can be distinguished and use separately or two or more mixing use.Its consumption accounts for 0～40 (wt) % of fire retardant total amount, more preferably 0～25 (wt) %.
The preparation of a kind of halogen-free expansible polyolefine of the present invention incombustible agent comprises that ammonium polyphosphate 70 weight % that the above-mentioned Racemic glycidol amine epoxy resin that obtains is coated and inorganics 10 weight % and triaizine compounds or derivatives thereof 20 weight % thorough mixing in mixing machine make (embodiment 1); Perhaps ammonium polyphosphate 40 weight % that the above-mentioned Racemic glycidol amine epoxy resin that obtains is coated and inorganics 40 weight % and triaizine compounds or derivatives thereof 20 weight % thorough mixing in mixing machine make (embodiment 2); Perhaps ammonium polyphosphate 95 weight % that the above-mentioned Racemic glycidol amine epoxy resin that obtains is coated and inorganics 1 weight % and triaizine compounds or derivatives thereof 4 weight % thorough mixing in mixing machine make (embodiment 3); Perhaps ammonium polyphosphate 80 weight % and the inorganics 20 weight % thorough mixing in mixing machine that the above-mentioned Racemic glycidol amine epoxy resin that obtains is coated makes (embodiment 4).
Polyolefine incombustible agent of the present invention is applied in the polymkeric substance, and the content of following polymers is at 50～85 (wt) %, more preferably 60～80 (wt) %.
(A) polymkeric substance of single and diolefin, as: high, medium and low density, crosslinked polyethylene, the polymkeric substance of polypropylene, polyisobutene, polybutene-1, polymethylpentene-1, polyisoprene, polyhutadiene and cycloolefin such as cyclopentenes, norbornylene etc.
(B) above-mentioned (A) mixture of polymers of being introduced is as polyethylene and polyacrylic mixture.
(C) between monoolefine or the diolefin, or with other the multipolymer of vinyl monomer.As: ethylene/propene copolymer, propene/but-1-ene copolymer, the multipolymer of propylene/isobutylene copolymers, ethene/isobutylene copolymers, ethylene/butylene-1 multipolymer, propylene/butadienecopolymer, iso-butylene/isoprene copolymer, ethylene/alkyl acrylate copolymers, ethylene/alkyl alkylmethacrylate polymer, ethylene/vinyl acetate multipolymer, ethylene/acrylic acid copolymer and their salt (ionomer), ethene and propylene and diolefine.
Making the satisfied polymkeric substance of people is monoolefine polymer, particularly PP, EVA, PE etc.
In the flame retardancy polyolefin resin constituent of the present invention, relative 100 parts of polyolefin resines, (A), the total addition level of (B), (C) is for for 15%～50% of moulding usefulness constituent total amount, is preferably 15～35%.When this can guarantee that polymkeric substance has certain flame retardancy, mechanics of machinery and electrical property that can also less impact polymer.
Constituent of the present invention can be allocated additives such as oxidation inhibitor, photostabilizer, softening agent, whipping agent, lubricant, static inhibitor, remover, tinting material and filler into according to actual needs.
The manufacture method of the constituent of flame retardancy polyolefin resin of the present invention, can form by the prescription of defined, with melting mixings such as cylinder machine, kneader, mixing roll, single screw extrusion machine, twin screw extruders, again according to the form of purpose moulded products, with various shaper forming process.
Following apparatus system is equipped with the component (1) in the example explanation present composition, the i.e. manufacture method of Racemic glycidol amine epoxy resin coated ammonium polyphosphate.
Preparation example 1
In the reactor that heated and stirred, reflux are housed, add 1.8L methyl alcohol and 1kg APP, under agitation be heated to 67 ℃, drip simultaneously then and contain the methanol solution 0.56L of tricyanic epoxy resin and the methanol solution of 0.02L diethylene diamine, about 30 minutes of stirring reaction falls about still temperature to 40 ℃ then, filter, filter cake is dry under 90 ℃/30mmHg condition, obtains the APP1.12kg that the good tricyanic epoxy resin of free-flowing property coats, and is called A1.
Preparation example 2
In the reactor that heated and stirred, reflux are housed, add 2L ethanol and 1kgAPP, under agitation be heated to 80 ℃, add the ethanolic soln 0.6L that contains aniline Resins, epoxy then earlier, add the ethanolic soln of 0.02L quadrol after stirring again, continued stirring reaction about 30 minutes, fall then about still temperature to 50 ℃, filter, filter cake is dry under 90 ℃/30mmHg condition, obtain the APP1.2kg that the good aniline Resins, epoxy of free-flowing property coats, be called A2.
With the composite flame retardancy that just can bring into play excellence of the composition in the above-mentioned incombustible agent system, can obtain the excellent flame retardancy polyolefin resin constituent of halogen-free expandable self-extinguishing, this incombustible agent equally also is applicable to the polyolefin resin constituent that contains whipping agent, thermosol etc.
Below with application example and comparative example the present invention is specified.
Flame retardancy and mechanical property evaluation result are shown in following table.
| Gradation composition (wt) | Application example | Comparative example | ||||||||||
| 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | 9 | 10 | 11 | 12 | |
| PP | 72 | 72 | 72 | 72 | 72 | 72 | 72 | 72 | 72 | 72 | 72 | 72 |
| APP | 20 | 20 | 20 | |||||||||
| A1 | 20 | 20 | 20 | 20 | 20 | |||||||
| A2 | 20 | 20 | 20 | 20 | ||||||||
| Silicon-dioxide | 4 | |||||||||||
| Calcium oxide | 4 | |||||||||||
| Talcum powder | 3 | 8 | ||||||||||
| Molecular sieve | 8 | 3 | 3 | |||||||||
| Zeolite | 8 | 3 | ||||||||||
| Zircon sand | 3 | |||||||||||
| Titanium dioxide | 3 | |||||||||||
| Zinc | 3 | 3 | ||||||||||
| Melamine | 5 | 5 | ||||||||||
| Melamine cyanurate | 5 | 5 | 5 | 5 | ||||||||
| The reactant of trihydroxyethyl cyanurate and TDI | 5 | |||||||||||
| The reactant of trihydroxyethyl cyanurate and terephthalic acid | 5 | |||||||||||
| The standard additive | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
| UL-94 | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 | V-1 | V-1 | V-1 |
| Tensile strength (Mpa) | 34.5 | 34.7 | 34.3 | 34.6 | 32.1 | 33.4 | 35.1 | 34.8 | 35.0 | 31.8 | 31.5 | 32.9 |
| Elongation at break (%) | 35 | 34 | 36 | 37 | 38 | 36 | 40 | 35 | 38 | 33 | 32 | 34 |
| Simply supported beam notched Izod impact strength (KJ/m3) | 11.8 | 11.3 | 10.6 | 11.6 | 11.9 | 11.5 | 11.7 | 11.9 | 11.4 | 9.4 | 9.6 | 9.5 |
Claims (10)
1. halogen-free expansible polyolefine incombustible agent is characterized in that this incombustible agent comprises the component of following weight content:
(1) Racemic glycidol amine epoxy resin coated ammonium polyphosphate 40～95%,
(2) inorganics 1～40%,
(3) the triaizine compounds or derivatives thereof 0～40%,
Wherein the covering amount of Resins, epoxy is 0.5～25wt% of ammonium polyphosphate in the component (1).
2. a kind of halogen-free expansible polyolefine incombustible agent according to claim 1 is characterized in that described Racemic glycidol amine epoxy resin is selected from one or both in tricyanic epoxy resin, the aniline Resins, epoxy.
3. a kind of halogen-free expansible polyolefine incombustible agent according to claim 1 is characterized in that the molecular formula of described ammonium polyphosphate is (NH
4PO
3)
n, n=50 in the formula～1000.
4. a kind of halogen-free expansible polyolefine incombustible agent according to claim 1, it is characterized in that described inorganics is selected from one or more in talcum powder, carclazyte, wollastonite, zeolite, silico-aluminate, molecular sieve, kaolin, zircon sand, polynite, mica, wilkinite, lime carbonate, calcium sulfate, silicon-dioxide, calcium oxide, boron trioxide, ammonium borate, ammonium silicate, Calucium Silicate powder, titanium dioxide, antimonous oxide, magnesium oxide, aluminum oxide, aluminium hydroxide, brucite, magnesium hydroxide, the basic carbonate calcium.
5. according to claim 1 or 4 described a kind of halogen-free expansible polyolefine incombustible agents, it is characterized in that described inorganics can adopt coupling agent and/or tensio-active agent that it is carried out surface treatment.
6. a kind of halogen-free expansible polyolefine incombustible agent according to claim 5, it is characterized in that described coupling agent and/or tensio-active agent are selected from one or more in silane coupling agent, titanate coupling agent, aluminate coupling agent, nonionogenic tenside, cats product, the fluorochemical surfactant.
7. a kind of halogen-free expansible polyolefine incombustible agent according to claim 1, it is characterized in that, described triaizine compounds or derivatives thereof is selected from the compound that contains triazine ring in the molecule, comprises in melamine, tri methylol melamine, melamine cyanurate, melamine phosphate, bis phosphoric acid tetramethylolmethane melamine salt, guanamine, phenylpropyl alcohol guanamine, methyl guanamines, succinyl-guanamines, the acid of cyanogen urea, trishydroxymethyl cyanurate and derivative, trihydroxyethyl cyanurate and derivative thereof, three-glycidyl isocyanuric acid ester and the derivative thereof one or more.
8. the preparation method of a halogen-free expansible polyolefine incombustible agent is characterized in that, this method comprises following processing step:
(1) preparation of Racemic glycidol amine epoxy resin coated ammonium polyphosphate
(a) at first in the reactor that has heated and stirred, reflux condensate device, add Resins, epoxy and organic solvent or water, heating makes the Resins, epoxy dissolving, adds the ammonium polyphosphate back that stirs then and adds solidifying agent; Perhaps the ammonium polyphosphate powder suspension in organic solvent or water, add Resins, epoxy and the solidifying agent that has been dissolved in the organic solvent simultaneously or successively, wherein the covering amount of Resins, epoxy is 0.5～25 weight % of ammonium polyphosphate;
(b) insulation reaction postcooling, filtration, washing, drying obtain the Resins, epoxy coated ammonium polyphosphate, and the reaction times is 0.5～2 hour;
(2) preparation of polyolefine incombustible agent
Ammonium polyphosphate 40～95 weight % and inorganics 1～40 weight % and triaizine compounds or derivatives thereof 0～40 weight % thorough mixing in mixing machine that the Racemic glycidol amine epoxy resin that step (1) is obtained coats make a kind of halogen-free expansible polyolefine incombustible agent.
9. the preparation method of a kind of halogen-free expansible polyolefine incombustible agent according to claim 8 is characterized in that described organic solvent is selected from one or more among methyl alcohol, ethanol, Virahol, acetone, tetrahydrofuran (THF), the DMF.
10. the preparation method of a kind of halogen-free expansible polyolefine incombustible agent according to claim 8 is characterized in that, described solidifying agent is selected from one or more in amine curing agent, acid anhydride type curing agent and the high score subclass solidifying agent.
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| CN 200310122097 CN1257219C (en) | 2003-12-30 | 2003-12-30 | Halogen less expansion type polyolefine incombustible agent and its preparation method |
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| CN100378160C (en) * | 2005-07-12 | 2008-04-02 | 南京航空航天大学 | Non-halogen fire-retardant polypropylene and production thereof |
| CN100400592C (en) * | 2006-12-08 | 2008-07-09 | 浙江大学 | Fire tetardant no-halogen epoxy resin glue and its prepn process and use |
| CN101434843B (en) * | 2007-11-16 | 2011-12-14 | 上海化工研究院 | Halogen-free expansion type flame retardant containing macromole triazine charring agent and preparation thereof |
| CN101550249B (en) * | 2008-04-02 | 2012-07-18 | 上海化工研究院 | Halogen-free expandable fire retardant fiber glass reinforced polypropylene material and preparation method thereof |
| CN105778264B (en) * | 2014-08-11 | 2020-06-02 | 江苏理工学院 | Preparation method of halogen-free flame-retardant POE material |
| CN105348978A (en) * | 2015-12-11 | 2016-02-24 | 江苏国泰环境监测有限公司常熟分公司 | Tail-gas detection device |
| CN106046422A (en) * | 2016-07-21 | 2016-10-26 | 肖金源 | Incombustible fire-resistant treating agent |
| CN108586805A (en) * | 2018-05-23 | 2018-09-28 | 芜湖航天特种电缆厂股份有限公司 | Cable fire-retardant combination and preparation method thereof |
| CN115536915B (en) * | 2022-10-31 | 2023-07-25 | 无锡市弘远塑业科技有限公司 | Low-atomization calcium-zinc stabilizer for PVC and stability test method thereof |
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