CN1281001A - Anti-hydrolysis organophosphoric deoxidant - Google Patents
Anti-hydrolysis organophosphoric deoxidant Download PDFInfo
- Publication number
- CN1281001A CN1281001A CN 99109783 CN99109783A CN1281001A CN 1281001 A CN1281001 A CN 1281001A CN 99109783 CN99109783 CN 99109783 CN 99109783 A CN99109783 A CN 99109783A CN 1281001 A CN1281001 A CN 1281001A
- Authority
- CN
- China
- Prior art keywords
- hydrolysis
- coupler
- metal
- salt
- organic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Abstract
An anti-hydrolysis organophosphoric deoxident contains organic phosphite or phoshite compound (20-99.9 wt%) and acidifying agent of metallic salt (0.1-80 wt%), which has been treated by surface-treating agent chosen from silane coupling agent, titanate coupling agent, zirconate coupling agent, aluminate coupling agent, zirconate-aluminate coupling agent and non-ionic or anionic surfactant.
Description
The present invention relates to a kind of organic phosphorous antioxidant that can anti-hydrolysis, particularly relates to a kind of antioxidant that can be used to improve the antioxidant effect of resin under the high aqueous environment of high temperature.
Generally speaking, organic phosphorous antioxidant produces phosphoric acid in the easy hydrolysis of the environment of high temperature, high-moisture, decompose the hydrolysis rate that the phosphoric acid that is produced can further quicken phosphorous antioxidant again, so not only can reduce the oxidation-resistance of composition, also can cause the damage of equipment, cause the pollution that to expect even; In order to improve aforesaid drawbacks, usually can in reaction, add the speed that the amine organic compound reduces the phosphorous antioxidant hydrolysis, aforementioned amine organic compound is for example: vulkacit H, three Isopropamides, dimethyl stearylamide etc., but the poor effect that these compounds improve, and the existence of amine can influence the chemical property and the toxigenicity of resin, and is therefore unsatisfactory in the use; In addition, the amine organic compound for example normally cooperates: trisnonyl phenyl phosphite, phenylbenzene phosphorous acid isodecyl ester, the different monooctyl ester of phenylbenzene phosphorous acid, triphenyl phosphite, 4,4 '-isopropylidene phosphorous acid dihydroxyphenyl alkane (C
12-C
15) ester [4,4 '-iso prpylidene diphenol alkyl (C
12-C
15) phosphite)] etc. the antioxidant of liquid phosphide use.
The method that a kind of anti-hydrolysis is arranged in addition is ortho-substituent sterically hindered with protection phosphorus of strengthening phenols, makes phosphorus be difficult for contacting with water molecules, effectively prevents the generation of hydrolysis phenomenon whereby; For example: the trade name of Ciba company is the antioxidant of Irgafos 168: tricresyl phosphite (2, the 4-dibutyl) phenyl ester [Tris-(di-tert-butyl-2,4-phenyl) phosphite], just having the tert-butyl substituents phenols by three at the ortho position is formed, the following formula I of its structural formula, though the hydrolysis phenomenon that antioxidant produced with following formula I seldom, but because this composition has reduced the affinity of phosphorous antioxidant to oxygen, reduced resistance to oxidation simultaneously, therefore, the phosphorous antioxidant that often must add volume just can reach identical effect, and is also undesirable in the use.
In order to improve aforesaid drawbacks; U.S.'s patent of invention the 5th; 856; No. 550 patent cases propose the method for another anti-hydrolysis; be exactly in organic phosphorous antioxidant, to add inorganic antacid; and together use aminated compounds to reach the purpose of anti-hydrolysis; above-mentioned inorganic antacid is for example: metal oxide; carbonic acid metal salt; carboxylic metallic salt; hydrotalcite; zeolite etc.; together use inorganic relieving haperacidity ester and tri-isopropanolamine; absorb the phosphoric acid that is produced after organic phosphorous antioxidant hydrolysis; under sour environment, produce the phenomenon of quickening hydrolysis to reduce it; and because the affinity between inorganic antacid and organo phosphorous compounds is not good; therefore; disperseing still can't to protect the phosphorous antioxidant compound effectively, in addition under the uneven situation; the interpolation of amine organic compound also can cause resin form and aspect variation; the processing variable color; problems such as toxigenicity.
On the other hand, U.S.'s patent of invention the 4th, 810, No. 579 and the 5th, 326, patent cases such as No. 803, utilize the response type coupler to be coated on the organo phosphorous compounds surface, borrow coupler that the hydrophobicity of water is reached the effect of anti-hydrolysis, more than two kinds of resistance to hydrolysiss that method perhaps helps the powdery organo phosphorous compounds to store under high humidity environment, but if under the condition of high temperature and high humidity more than 200 ℃, still can't reach the effect of anti-hydrolysis, for example after this kind organo phosphorous compounds and the mixed with resin, under the condition of high humidity/high temperature (more than 100 ℃), when adding in the forcing machine mixing extruding, aforementioned two kinds of methods all can't reach the effect of anti-hydrolysis.
This case contriver etc. will overcome problem point exactly, improves at the composition of organic phosphorous antioxidant, makes it under the condition of high temperature, high humidity, still has good anti-hydrolysis effect.
The object of the present invention is to provide a kind ofly to have the good resistance hydrolysis effect, and be added in the resin when mixing, also can produce good form and aspect, and not have organic phosphorous antioxidant of shortcomings such as processing variable color and toxigenicity.
Another object of the present invention is to: a kind of processibility and oxidation-resistance that improves after composition and the mixed with resin is provided, and composition and carrier hybrid shaping directly can be made an addition to organic phosphorous antioxidant of processing in the resin.
The invention is characterized in: a kind of organic phosphorous antioxidant is provided, above-mentioned antioxidant comprises: organophosphite, perhaps organic phosphinate (phosphonite), and the metal-salt antacid of handling through surface treatment agent, can add carrier in case of necessity, make its formation a kind of under hot and humid environment, still have the antioxidant of good resistance to hydrolysis and oxidation-resistance, above-mentioned antioxidant and can be directly as the additive use of polymkeric substance.
Organic phosphorous antioxidant of the present invention is to comprise:
(a) organophosphite of 20～99.9wt% or phosphinate compound; And
(b) 0.1～80wt% is through the metal-salt antacid of surface treatment agent processing;
Wherein, the weight ratio of surface treatment agent and metal-salt antacid is 0.1～50wt%/99.9～50wt%, and surface treatment agent is selected from: silane is that coupler, titanate are that coupler, zirconate are coupler, aluminate-series coupler, zirconium-aluminate-series coupler, non-ionic interfacial agent and anionic interfacial agent.
Phosphorous acid ester of the present invention is meant to have P (OR)
3The compound of formula, wherein, the R representation hydrocarbyl, it can include heteroatoms, and has two can be replaced by hydrogen atom at most among 3 R, and heteroatoms other atoms except carbon atom and hydrogen atom all can, be preferably nitrogen, oxygen, fluorine, silicon, phosphorus, sulphur, chlorine, bromine, tin and iodine.
Phosphinate is meant the compound of phosphonous acid through esterification, and above-claimed cpd has P (OR)
2The formula of R, wherein the group of R representative is described identical with leading portion, maybe can be halogen; Preferably a kind of solid of phosphorous acid ester of the present invention or phosphinate (in the time of 20 ℃), it often is a kind of crystalline solid.
The object lesson of phosphorous acid ester of the present invention has: tricresyl phosphite (dimethyl) phenyl ester, tricresyl phosphite (uncle's octyl group) phenyl ester [tri (t-octylphenyl) phosphite], trisnonyl phenyl phosphite [being called for short TNPP], tricresyl phosphite (22) alkane ester, phosphorous acid monobutyl dioctyl ester, tribenzyl phosphite, phosphorous acid monobutyl diphenyl, phosphorous acid list nonyl phenyl dioctyl ester, phosphorous acid list hexyl diisopropyl ester, phosphorous acid cyclohexyl two (18) alkyl ester, diphosphite phenylbenzene neo-pentyl ester, phosphorous acid diisooctyl octyl octylphenyl, four (nonyl phenyl) diphosphite propylene alcohol ester, three phosphorous acid seven (dipropylene glycol) esters [heptakis (dipropyleneglycol) triphosphite], phosphorous acid gathers (dipropylene glycol) phenyl ester, two (stearyl) pentaerythritol ester [the bis stearyl pentaerythritol diphosphite of diphosphorous acid, hereinafter to be referred as BSPDP], diphosphite-2,2-dimethyl propylene alcohol ester, hydrogen phosphite two lauryls, the two octyl group esters of hydrogen phosphite, two octadecyl phosphorous acid hydrogen esters, the phosphorous acid trihydroxymethylpropanyl ester, 2,2-dimethyl-1,3-propenyl-phosphorous acid lauryl, the tricresyl phosphite phenylester, the tricresyl phosphite cyclohexyl ester, the tricresyl phosphite ethyl ester, tricresyl phosphite octyl group ester, the tricresyl phosphite polyhexamethylene, tricresyl phosphite (dodecyl ester), tricresyl phosphite (18) alkyl ester, phosphorous acid tris(1-methylethyl) ester, tricresyl phosphite (tertiary butyl ester), tricresyl phosphite (2-ethyl) polyhexamethylene, Tritolyl Phosphate, phenylbenzene phosphorous acid (2-ethyl) polyhexamethylene, triphenyl phosphite, tricresyl phosphite (2, the 5-di-t-butyl) phenyl ester, tricresyl phosphite (the 2-tertiary butyl) phenyl ester, tricresyl phosphite (2-phenyl) phenyl ester, [2-(1 for tricresyl phosphite, the 1-dimethyl propyl)] phenyl ester, tricresyl phosphite (2-cyclohexyl) phenyl ester, tricresyl phosphite (the 2-tertiary butyl-4-phenyl) phenyl ester, tricresyl phosphite (the 2-tertiary butyl-4-methyl) phenyl ester, tricresyl phosphite (2,4-two tert-pentyls) phenyl ester, tricresyl phosphite (2, the 4-di-t-butyl) phenyl ester, diphosphorous acid two (2, the 4-di-tert-butyl-phenyl) pentaerythritol ester, diphosphorous acid-two (stearyl) pentaerythritol ester, tricresyl phosphite (blended list and two nonyl) phenyl ester [tri (mixed mono-anddinonylphenyl) phosphite], 4,4 '-isopropylidene-dihydroxyphenyl-phosphorous acid alkyl (C
12-C
15) ester, phenylbenzene phosphorous acid isodecyl ester, phenylbenzene-phosphorous acid isooctyl acrylate etc.
Organic phosphinate compound of the present invention has: phenyl-phosphonite diethyl ester, octyl group phosphonous acid dibutylester, decyl phosphonous acid diisopropyl ester, hexyl phosphonous acid di tert butyl carbonate, dodecyl phosphonous acid dioctyl ester, cyclohexyl phosphonous acid dioctyl ester, lauryl phosphonous acid diphenyl, phenyl-phosphonite two cyclohexyls, nonyl phenyl phosphonous acid two nonylbenzene esters, stearyl phosphonous acid benzhydryl ester, the two phosphonous acid neo-pentyl esters of dioctyl etc.
Metal-salt antacid of the present invention can be: metal-salt, hydrotalcite, zeolite or its mixture of carbonate, two carbonate, carboxylate salt, oxide compound, oxyhydroxide, phosphite, boric acid ester (borates), aforementioned metal are I A, II A, III A, IV A and the rare earth metals etc. that are selected from the periodictable; The object lesson of above-mentioned metal-salt antacid has: aluminum oxide, talcum, hydrotalcite, zeolite, silica, montmorillonite, montmorillonite, magnesium oxide, calcium oxide, rare earth oxide, magnesium hydroxide, calcium hydroxide, lime carbonate (Ca
2O
3), calcium acetate and magnalium boric acid ester, be preferable wherein with zeolite and hydrotalcite, the metal-salt with zeolite system is the best especially.
Be suitable for zeolite of the present invention and have following logical formula II:
xM
N[x(AlO
2)·y(SiO
2)]·w(H
2O)-----Ⅱ
Wherein, N is the cationic charge of M, and M is the metal among I A or the II A in the periodictable, is meant sodium, potassium, magnesium and/or calcium especially; Y/x is 0.8～1.2 numeral, and w is 0.5～50 numeral.
Suitably the typical example of zeolite has following empirical formula:
12Na[12(AlO
2)·12(SiO
2)]·12(H
2O)
4．5Ca·3Na[12(AlO
2)·12(SiO
2)]·30(H
2O)
9K·3Na[12(AlO
2)·12(SiO
2)]·27(H
2O)
Being suitable for zeolite type of the present invention has the illiteracy of types such as A, X, Y, L, Z S M 5,11,22,23 to draw a zeolite, Europe clothes to draw and take many zeolites, grey garranite, side's nahcolite, organic zeolite, and materials such as ALPO class or SAPO class, wherein the zeolite with A, X, Y type is good, more with the zeolite of A type for better.
The metal-salt antacid of handling through surface treatment agent is to be scattered in organophosphite or the phosphinate composition with the following particle of 50 μ m, is good with the following particle of 20 μ m wherein, more being the best below the 2 μ m; When the particle diameter of metal-salt antacid when 100 μ m are above, the resistance to hydrolysis of organic phosphorous antioxidant is not good, and is wherein, poorer under the condition of high temperature, high humidity.
Be used in hydrotalcite of the present invention and have following logical formula III:
(1-x)M
(2+)·xM
(3+)·2(OH)·(x／n)A
(n-)·pH
2O-----Ⅲ
Wherein, M
(2+)Representative: magnesium, calcium, strontium, barium, zinc, lead, tin and/or nickel, M
(3+)Represent aluminium, boron, bismuth, A
(n-)Represent the negatively charged ion of n valency, and n is meant 1 to 4, x is meant 0 to 0.5, and p is meant O to 2, and A can be: OH
-, Cl
-, Br
-, I
-, ClO
-4, NCO
3 -, CH
3COO
-, C
6H
5COO
-, CO
3 -2, SO
4 -2, (CHOHCOO)
2 -2, (CHOH)
4CH
2OHCOO-, C
2H
4(COO)
2 -, (CH
2COO)
2 -2, CH
3CHOHCOO-, SiO
3 -2, SiO
4 -4, Fe (CN)
6 -3, Fe (CN)
6 -4, BO
3 -3, PO
3 -3Or HPO
4 -2
The hydrotalcite that other can use very easily in above-mentioned technology, then be have following general formula (III a):
xM
(2+)·Al
2·(2x+6nz)(OH)·2A
(n-)·pH
2O-----Ⅲa
Wherein, the M among the general formula III a
(2+)Be at least a a kind of, be preferably magnesium by selecting in the metals of the same clan such as magnesium or zinc, and A
(n-)Be meant negatively charged ion, particularly be selected from CO
3 2-And S
2-, aforementioned anionic valence is n, and p is positive integer, and the best is 0.5 to 5, and x and z are positive integers, and x is preferably 2 to 6, and z then is less than 2.
Preferable in the present invention hydrotalcite is the compound with logical formula III, wherein, and M
(2+)Be calcium or magnesium, or the solution of solid-state magnesium or zinc, and A
(n-)Be CO
3 (2-), BO
3 (3-)Or PO
3 (3-), x is 0 to 0.5 numeral, and p is 0 to 20, and they are M of metal-salt
(3+)Be preferable particularly with aluminum ion.
According to observing or the experimental result demonstration, the object lesson that is specially adapted to hydrotalcite preferable among the present invention has:
Being suitable for surface treatment agent of the present invention is to be selected from: silane is that coupler, titanate (Titanate) are that coupler, zirconate (Zirconate) are that coupler, aluminate (Aluminate) are that coupler, zirconium-aluminic acid (Zirco-Aluminate) salt are coupler, non-ionic interfacial agent and anionic interfacial agent etc., be preferable with silane system and non-ionic interfacial agent again wherein, the best is a coupler for silane; Above-mentioned titanate is that the concrete example of coupler has: three stearyl-isopropyl titanates, three (dioctyl pyrophosphoryl base) isopropyl titanate, two dioctyl (pyrophosphoryl base) esters [bis dioctyl (pyrophosphate) oxyacetate titanate] of fluoroacetic acid base metatitanic acid, two (the dioctyl pyrophosphoryl base) esters of vinyl metatitanic acid, two dioctyl (inferior phosphoryl) titanium isopropylate, two [two (the inferior phosphoryl of three decyls)] metatitanic acid ester in four last of the ten Heavenly stems etc.
And being the object lesson of coupler, silane has: γ-An Bingjisanjiayangjiguiwan, γ-An Bingjisanyiyangjiguiwan, γ-aminopropyl methyldiethoxysilane, N-β-aminoethyl-γ-aminopropyl-Trimethoxy silane (N-β-aminoethyl-γ-aminopropyltrimethoxy silane), N-β-aminoethyl-γ-aminopropyl-methyl-dimethoxy silane, 4,5-dihydro base-1-[3-(three ethoxies are silica-based) propyl group] imidazoles, γ-mercaptopropyl trimethoxysilane, γ-mercapto propyl group methyl dimethoxysilane, γ-glycidoxypropyltrime,hoxysilane, γ-methacryloyl Trimethoxy silane, γ-r-chloropropyl trimethoxyl silane, γ-chloropropyl triethoxysilane, gamma-chloropropylmethyldimethoxysilane, vinyltrimethoxy silane, vinyltriethoxysilane, and vinyl three ('beta '-methoxy oxyethyl group) silane; Wherein, be preferable with vinyltrimethoxy silane or its analogue.
The example that non-ionic interfacial agent is concrete has: propylene glycol stearate, the distearyl acid propylene glycol ester, Tego-stearate, sesquialter oleic acid sorbitol ester (sorbitanmono-octadecanoate), three sorbitan monostearates, single palmitinic acid macrogol ester, polyoxyethylene glycol, polypropylene glycol, distearyl acid polyethylene glycol ester, two oleic acid macrogol esters (polyethylene glycol di-octadecanoic ester), the lanolin fatty acid macrogol ester, three stearic acid polyoxyethylene glycol sorbitol esters, coco-nut oil fatty acid polyoxyethylene glycol acid amides, Voranol EP 2001, polyoxyethylene polyoxy-propylene, coconut oil fatty acid monoethanolamide, stearic acid monoethanolamide, Stearic acid diethanolamine salt.The polyoxyethylene phenyl ether (can have substituting group on the phenyl ring, for example isobutyl-, octyl group), multipolymer, polyvinylpyrrolidone and the analogue thereof of polyoxyethylene octyl phenyl ether, vinyl acetate between to for plastic and vinyl alcohol, wherein, and preferable with Voranol EP 2001, polyoxyethylene polyoxy-propylene, polyoxyethylene phenyl ether.
The object lesson of anionic interfacial agent has: alkyl sodium sulfonate, Voranol EP 2001 sodium sulfonate, polyoxyethylene Phenylsulfonic acid, polyxyethylated phosphoric acid (alkylpolyoxyethylene phosphonic acid), polyoxyethylene alkylphenyl phosphoric acid, polyoxyethylene alkylphenyl tricresyl phosphate ethanol ester, lecithin.
The interfacial agent that is suitable for the present invention is except can being selected from aforementioned non-ionic interfacial agent and anionic interfacial agent, also can be selected from cationic interfacial agent, and two ionic interfacial agent, be good with non-ionic interfacial agent and anionic interfacial agent wherein, the best is a non-ionic interfacial agent.
The usage quantity of above-mentioned surface treatment agent and inorganic salt antacid adds up to 100wt%, and the ratio between surface treatment agent and metal-salt antacid is 0.1～50wt%/99.9～50wt%, is preferable with 2～25wt%/98～75wt% wherein; When the weight ratio of surface treatment agent and metal-salt antacid when 0.1wt%/99.9wt% is following, the metal-salt antacid is that dispersion effect in the antioxidant is not good at organic phosphoric acid, resistance to hydrolysis is also relatively poor, and both weight ratios are not inconsistent economic benefit when 50wt%/50wt% is above.
Through the surface-treated metal-salt antacid of surface treatment agent, its preparation method can be put into airtight mixing tank with metal-salt antacids such as zeolite, hydrotalcite and surface treatment agent, produces coating reaction to guarantee surface treatment agent and zeolite or hydrotalcite in the surface through thorough mixing.Other preparation method also can become muddy with solvent with zeolite (or hydrotalcite), adds after surface treatment agent mixes again, and making dry finished product, but aforementioned preparation should be in operation below 100 ℃ removal of solvents.
Organic phosphorous antioxidant of the anti-hydrolysis of the present invention can further add carrier to be mixed, and via compressing tablet, extrude or granulation is finished.Be suitable for the essentially no any restriction of carrier of the present invention, but with the resin treatment accessibility, its fusing point is to be good with the high organism of more organic phosphorous antioxidant, for example: Poly Propylene Wax, polyethylene wax, ethylenebisstearamide (ethylenebis-stearamide, be called for short EBA), lubrication prescription, processing aid, and (phenol system) or secondary (sulphur system once, phosphorus system, bulky amine system) antioxidant, as tetramethylene-3-(3 ', 5 '-di-tert-butyl-hydroxy phenyl) methyl propionate [Tetra kis methylene-3-(3 ', 5-di-tert-butyl-4-hydroxy phenyl) propionate methane] or tricresyl phosphite (2, the 4-dibutyl) phenyl ester [Tris-(di-tert-butyl-2,4-phenyl) phosphite] etc.The addition of above-mentioned carrier is with respect to 0～200 weight part in the antioxidant of 100 weight parts, wherein, is preferable with 25～150 weight parts again.
Another purpose of the present invention is: make organic high molecular polymer add the organic phosphorous antioxidant and the aforesaid carrier of aforementioned anti-hydrolysis, can obtain that resistance to hydrolysis is good, the organic polymer composition of good, the anti-processing thermally denature of polymkeric substance form and aspect excellence.Above-mentioned organic high molecular polymer can be: polyene system, polystyrene, poly-diene system, polycarbonate-based, polyester system or its mixture etc., and wherein, the polyene based polymer includes: polypropylene, polyethylene, polyvinyl chloride, polymethylmethacrylate etc.; And polystyrenic polymer comprises: the multipolymer of polystyrene, impact resistance phenylethylene, acrylonitrile-butadiene-styrene copolymer, acrylonitritrile-styrene resin, MBS, acrylic ester-acrylonitrile-styrol copolymer, ethylene-propylene-diene rubber and acrylonitrile-styrene etc.; And diene polymers includes: homopolymer or multipolymers such as divinyl, isoprene and chloroprene, the polycarbonate based polymer includes: polycarbonate, the polyester based polymer includes: polyethylene terephthalate, polybutylene terephthalate etc.
High molecular polymer of the present invention is the organic high molecular polymer of water content more than 2%, the organophosphite of aforementioned polymer and anti-hydrolysis or phosphinate, and add an amount of carrier, according to certain proportion through having the forcing machine mixing extruding pelletization of dehydration equipment, just can make organic polymer composition, the temperature of above-mentioned forcing machine is set in 180～300 ℃; Polymer emulsion dewaters with centrifugal drier in the back of condensing, make it become the polymer powder of water content about 30%, in order to save the complicated operation of drying step and to reduce atmospheric pollution, the many directly fusion carriers of the polymer powder of aforementioned water content 30%, other polymkeric substance directly mixes devolatilization, to make water content at the polymkeric substance finished product below 0.5%.
Organic phosphorous antioxidant of the anti-hydrolysis of the present invention is specially adapted in the polymer processing processing of high temperature, high moisture content, especially under the state of water content more than 180 ℃, extrude mixing, not only the phosphorous antioxidant hydrolysis is few in the processing, the form and aspect of initial stage polymkeric substance are good, and heat-resistant stability is also good.
The following example is in order to exploitativeness of the present invention to be described, and is not to be used to limit scope of patent protection of the present invention.
Embodiment
Example 1 (anti-hydrolysis experiment)
Because the phosphorous acid that hydrolytic action generated can make potential of hydrogen (pH value) descend, so the variation that measures acidity and alkalinity can be learnt hydrolysing rate.
In 1 liter four-hole round bottom reaction flask, thermometer, mechanical stirrer, condenser, potential of hydrogen tester are housed, add the deionized water of 450 grams, the trisnonyl phenyl phosphite of 50.0 grams (0.100mole) (being called for short TNPP) successively as phosphorus compound, and being that the aluminum oxide handled of coupler or zeolite are as antacid through silane, start agitator and well heater afterwards until constant temperature (80 ℃), every pH-value of 1 hour record.
[table]
| Composition | Comparative example 1 | Embodiment 1 | Embodiment 2 |
| ????TNPP | ????50 | ????50 | ????50 |
| Deionized water | ????450 | ????450 | ????450 |
| Aluminum oxide is through the silane surface treatment | ????2．75 | ||
| Zeolite is through the silane surface treatment | ????2．75 | ||
| Hydrolytic resistance | ????× |
Silane/alumina weight in the last table is than=1/10, and silane/A type zeolite weight ratio=1/10, its weight average particle diameter is 0.5 μ m.
In the table * the expression hydrolytic resistance is poor, and zero expression hydrolytic resistance is good.
The variation of pH-value can be found significantly by the curve of aforementioned chart that as shown in Figure 1 anti-oxidant compositions of the present invention can effectively delay hydrolysis.
Example 2
Use two (stearyl) pentaerythritol esters of diphosphorous acid (being called for short BSPDP) to be phosphorus compound, various antacid, and be carrier with Irganox 1010, the composition of according to the form below two mix post-heating and are pressed into granularly, just can wait for the test rerum natura.Device with example 1, in five mouthfuls of round bottom reaction flasks of 1 liter, temperature regulator, mechanical stirrer, condenser, potential of hydrogen tester etc. are housed, keep temperature after pouring the deionized waters to 100 ℃ of 500 grams afterwards earlier into, pour 10 grams earnest to be measured then into, write down its pH value (0min), write down its pH value afterwards every 15 minutes, record the result as shown in Table 3.
[table two]
| The antioxidant kind | A | ?B | ?C | ?D | ?E | ?F | ?G | ?H | ?I |
| ????BSPDP | ?40 | ?40 | ?40 | ?40 | ?40 | ?100 | ?50 | ?0 | ?50 |
| ????Irganox?1010 | ?40 | ?40 | ?40 | ?40 | ?40 | ????0 | ?50 | ?0 | ?0 |
| ????Irgafos168 | ?100 | ||||||||
| DHT-4A-2 (without silane treatment) | 20 | ||||||||
| X type zeolite (without silane treatment) | 20 | ||||||||
| A type zeolite (through silane treatment) | 20 | ||||||||
| DHT-4A-2 (through silane treatment) | 20 | ||||||||
| MgO+DHT-4A-2 (through silane treatment) | 20 | ||||||||
| EBA (lubrication prescription) | 50 |
Annotate:
1, the title of Irganox 1010:CIBA company commodity, be that a kind of phenol is antioxidant, its chemical name is: tetramethylene-3-(3 ', 5 '-di-tert-butyl-hydroxy phenyl) methyl propionate [Tetra Kis methylene-3-(3 ', 5 '-di-tert-butyl-4-hydroxy phenyl) propionate methane].
2, MgO: Kyowaway 150 commodity that are Kyowa company.
3, DHT-4A-2:Kyowa company product, its be for
4.5MgAl
2(OH)
13CO
33.5H
2The hydrotalcite compound of O.
4, MgO and DHT-4A-2 mix through hydrotalcite surface treatment: MgO and DHT-4A-2/ silane=17/3.
5, A type zeolite is through silane treatment: silane/A type zeolite=2/18, its weight average particle diameter are 0.5 μ m.
6, the title of Irgafos 168:CIBA company commodity is a kind of phosphorous antioxidant, and its chemistry is by name: tricresyl phosphite (2, the 4-dibutyl) phenyl ester [Tris-(di-tert-butyl-2,4-phenyl) phosphite].
7, EBA: ethylenebisstearamide (it is a kind of lubrication prescription).
[table three]
| Experiment numbers | Embodiment 3 | Embodiment 4 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | ||
| Antioxidant | Kind | ????A | ????C | ????D | ????E | ????F | ????G | |
| Rerum natura | The pH measured value | 0 (minute) | ????7．8 | ????8．0 | ????3．6 | ????5．4 | ????2．5 | ????6．5 |
| 15 (minute) | ????7．6 | ????7．3 | ????4．0 | ????5．0 | ????1．7 | ????2．3 | ||
| 30 (minute) | ????7．3 | ????6．9 | ????3．4 | ????4．0 | ????1．6 | ????2．1 | ||
| 45 (minute) | ????7．0 | ????6．2 | ????3．0 | ????3．8 | ????1．5 | ????1．6 | ||
| Hydrolytic resistance | × | × | × | × | ||||
In the variation of aforementioned pH value, change more little and high more its hydrolytic resistance of demonstration of pH value better, and show by last table experimental data, composition of the present invention (embodiment 3,4) has good resistance to hydrolysis, though and comparative example 2 has used DHT-4A-2 type hydrotalcite, but because this hydrotalcite is without silane treatment, therefore, its resistance to hydrolysis is unsatisfactory; And comparative example 3 uses the X type zeolite without silane treatment, because its median size is the big particle diameter of 60 μ m, so itself and BSPDP and Irganox 1010 Combination are not good, causes resistance to hydrolysis not good.And comparative example 4 uses BSPDP (not adding antacid) fully, and comparative example 5 and with BSPDP and Irganox 1010 antioxidants such as (not adding antacid), and its anti-hydrolysis effect is also undesirable.
[example 3]
The antioxidant effect of thing of the present invention in resin is the standard of utilizing yellowness index (YI) to be used as measuring, for showing the excellent hydrolysis resistance and the oxidation-resistance of thing of the present invention, this example is to use ABS resin and the AS resin particle that contains 30% moisture content or 0.5% following moisture content respectively, and the different as shown in the following Table IV antioxidants of interpolation, the lubrication prescription mixture, at 230 ℃ with German W﹠PZSK-25 forcing machine extrusion granulator, wherein must remove moisture content and extrude ABS finished product grain through the devolatilization mouth, the finished product grain shakes the male mechanical system 40Z of society injection moulding machine SM-90 with Taiwan and injects in 210 ℃, diameter 55mm, the disk of thickness 3.2mm, again this disk is put the cooling back and surveyed its YI value with Gretoawacbeth color-eye 3100 spectrometers, other gets 2 disks of having surveyed YI and places the rotating disc type baking oven with 180 ℃ of high bakes after 2 hours, to be cooled, measure its YI value again, yellowness index difference before and after the baking oven test is exactly a △ YI value, and YI value and the △ YI value little expression oxidation-resistance that heals is better.
[table four]
| The experiment coding | Embodiment | Comparative example | ||||||||
| ????5 | ????6 | ????7 | ????8 | ????6 | ????7 | ????8 | ????9 | ????10 | ||
| ?ABS-1 | ????30 | ????30 | ||||||||
| ?ABS-2 | ?30 | ?30 | ?30 | ?30 | ?30 | ?30 | ?30 | |||
| ?AS | ????70 | ????70 | ????70 | ????70 | ????70 | ????70 | ????70 | ????70 | ????70 | |
| ?EBA | ????2 | ????2 | ????2 | ????2 | ????2 | ????2 | ????2 | ????2 | ????2 | |
| Antioxidant | Kind | ????A | ????B | ????A | ????B | ????E | ????F | ????G | ????H | ????I |
| Weight part | 0．15 | ?0．15 | ?0．15 | ?0．15 | ?0．15 | ?0．15 | ?0．15 | ?0．15 | ?0．15 | |
| Yellow chromaticity | YI | ????12 | ????13 | ?11．5 | ?12．4 | ?15．2 | ????18 | ????16 | ????17 | ????19 |
| △YI | ????30 | ????30 | ????29 | ????28 | ????36 | ????39 | ????38 | ????36 | ????40 | |
Annotate:
1, ABS1 is the acrylonitrile-butadiene-styrene copolymer (dry powder) of water ratio below 0.5%, and its addition is to calculate with dry weight.
2, ABS2 is the acrylonitrile-butadiene-styrene copolymer (wet-milling) of water ratio 30%, and its addition is to calculate with dry weight.
3, EBA: ethylenebisstearamide.
Embodiment by table four shows, phosphorous antioxidant does not have antioxidant effect after hydrolysis as can be known, and the YI of anti-oxidant compositions of the present invention and △ YI value are all preferable, and can improve the oxidation-resistance of resin, and can prevent the phosphorus series compound hydrolysis, have higher softening temperature effect, aforementioned antioxidant also has the oxidation-resistance that multiplies each other, and has industrial utilization.
Claims (21)
1, a kind of organic phosphorous antioxidant of anti-hydrolysis, it is characterized in that: this antioxidant comprises:
(a) organophosphite of 20～99.9wt% or phosphinate compound; And
(b) 0.1～80wt% is through surface treatment agent surface-treated metal-salt antacid;
Wherein, the weight ratio of surface treatment agent and metal-salt antacid is 0.1～50wt%/99.9～50wt%, and surface treatment agent is to be selected from: silane is that coupler, titanate are that coupler, zirconate are coupler, aluminate-series coupler, zirconium-aluminate-series coupler, non-ionic interfacial agent and anionic interfacial agent.
2, organic phosphorous antioxidant of anti-hydrolysis according to claim 1, it is characterized in that: surface treatment agent is that silane is coupler.
3, as organic phosphorous antioxidant of anti-hydrolysis as described in the claim 2, it is characterized in that:
Silane is that coupler is to be selected from: γ-An Bingjisanjiayangjiguiwan; γ-An Bingjisanyiyangjiguiwan; γ-aminopropyl methyldiethoxysilane; N-β-aminoethyl-γ-aminopropyl-Trimethoxy silane; N-β-aminoethyl-γ-aminopropyl-methyl-dimethoxy silane; 4; 5-dihydro base-1-[3-(three ethoxies are silica-based) propyl group] imidazoles; γ-mercaptopropyl trimethoxysilane; γ-mercapto propyl group methyl dimethoxysilane; γ-glycidoxypropyltrime,hoxysilane; γ-methylpropionyl Trimethoxy silane; γ-r-chloropropyl trimethoxyl silane; γ-chloropropyl triethoxysilane; gamma-chloropropylmethyldimethoxysilane; vinyltrimethoxy silane; vinyltriethoxysilane, and vinyl three ('beta '-methoxy) ethoxy silane.
4, as organic phosphorous antioxidant of anti-hydrolysis as described in the claim 3, it is characterized in that: silane is that coupler is vinyltrimethoxy silane and vinyltriethoxysilane.
5, organic phosphorous antioxidant of anti-hydrolysis according to claim 1, it is characterized in that: surface treatment agent is a non-ionic interfacial agent.
6, organic phosphorous antioxidant as anti-hydrolysis as described in the claim 5, it is characterized in that: non-ionic interfacial agent is to be selected from: propylene glycol stearate, the distearyl acid propylene glycol ester, the Stearinsaeure binaryglycol ester, sesquialter oleic acid sorbitol ester, three sorbitan monostearates, single palmitinic acid macrogol ester, polyoxyethylene glycol, polypropylene glycol, distearyl acid polyethylene glycol ester, two oleic acid macrogol esters, the lanolin fatty acid polyoxyethylene glycol, three stearyl polyoxyethylene glycol sorbitol esters, coco-nut oil fatty acid polyoxyethylene glycol acid amides, Voranol EP 2001, polyoxyethylene polyoxy-propylene, coconut oil fatty acid monoethanolamide, stearic acid monoethanolamide, Stearic acid diethanolamine salt, the polyoxyethylene phenyl ether (can have substituting group, for example isobutyl-on the phenyl ring, octyl group), polyoxyethylene octyl phenyl ether, the multipolymer of vinyl acetate between to for plastic and vinyl alcohol, polyvinylpyrrolidone and analogue thereof.
7, as organic phosphorous antioxidant of anti-hydrolysis as described in the claim 6, it is characterized in that: non-ionic interfacial agent is Voranol EP 2001, polyoxyethylene polyoxy-propylene, polyoxyethylene phenyl ether.
8, organic phosphorous antioxidant of anti-hydrolysis according to claim 1, it is characterized in that: the metal-salt antacid can be selected from: the metal-salt of carbonate, two carbonate, carboxylate salt, oxide compound, oxyhydroxide, phosphite, boric acid ester, hydrotalcite, zeolite or its mixture, aforementioned metal are I A, II A, III IA, IV A and the rare earth metals that is selected from the periodictable.
9, as organic phosphorous antioxidant of anti-hydrolysis as described in the claim 8, it is characterized in that: the metal-salt antacid is a hydrotalcite.
10, as organic phosphorous antioxidant of anti-hydrolysis as described in the claim 8, it is characterized in that: the metal-salt antacid is a zeolite.
11, as organic phosphorous antioxidant of anti-hydrolysis as described in the claim 10, it is characterized in that: the metal-salt antacid is an A type zeolite.
12, organic phosphorous antioxidant of anti-hydrolysis according to claim 1, it is characterized in that: the weight ratio of surface treatment agent and metal-salt antacid is 2～25wt%/98～75wt%.
13, organic phosphorous antioxidant of anti-hydrolysis according to claim 1 is characterized in that: the metal-salt antacid of handling through surface treatment agent is to be scattered in organophosphite or the phosphinate composition with the following particle of median size 50 μ m.
14, as organic phosphorous antioxidant of anti-hydrolysis as described in the claim 13, it is characterized in that: the median size of the metal-salt antacid of handling through surface treatment agent is below 20 μ m.
15, as organic phosphorous antioxidant of anti-hydrolysis as described in the claim 13, it is characterized in that: the median size of the metal-salt antacid of handling through surface treatment agent is below 2 μ m.
16, organic phosphorous antioxidant of anti-hydrolysis according to claim 1 is characterized in that: can further add carrier.
17, a kind of organic polymer composition, it is that the organophosphorus that comprises organic high molecular polymer and anti-hydrolysis is an antioxidant blends, above-mentioned antioxidant blends includes:
(a) organophosphite of 20～99.9wt% or phosphinate compound; And
(b) 0.1～80wt% is through the metal-salt antacid of surface treatment agent processing;
Wherein, the weight ratio of surface treatment agent and metal-salt antacid is 0.1～50wt%/99.9～50wt%, and surface treatment agent is selected from: silane is that coupler, titanate are that coupler, zirconate are that coupler, aluminic acid ester salt are coupler, zirconium-aluminate-series coupler, non-ionic interfacial agent and anionic interfacial agent.
18, organic polymer composition as claimed in claim 17 is characterized in that: organic high molecular polymer is polyene system, polystyrene, and poly-diene is that polycarbonate-based, polyester is or its phase mixture.
19, organic polymer composition as claimed in claim 17 is characterized in that: organic phosphorous antioxidant further can add carrier.
20, a kind of manufacture method of organic polymer composition, it is with the organic high molecular polymer of water content more than 2% and organic phosphorous antioxidant of anti-hydrolysis, extrude and get with the forcing machine mixing with devolatilization equipment, wherein organic phosphorous antioxidant of anti-hydrolysis comprises:
(a) organophosphite of 20～99.9wt% or phosphinate compound; And
(b) 0.1～80wt% is through coupler surface-treated metal-salt antacid;
Wherein, the weight ratio of surface treatment agent and metal-salt antacid is 0.1～50wt%/99.9～50wt%, and surface treatment agent is selected from: silane is that coupler, titanate are that coupler, zirconate are that coupler, aluminic acid ester salt are coupler, zirconium-aluminate-series coupler, non-ionic interfacial agent and anionic interfacial agent.
21, the manufacture method of organic polymer composition as claimed in claim 20 is characterized in that: the water content of this organic high molecular polymer is more than 5wt%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB991097831A CN1172981C (en) | 1999-07-15 | 1999-07-15 | Anti-hydrolysis organophosphoric deoxidant |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB991097831A CN1172981C (en) | 1999-07-15 | 1999-07-15 | Anti-hydrolysis organophosphoric deoxidant |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1281001A true CN1281001A (en) | 2001-01-24 |
| CN1172981C CN1172981C (en) | 2004-10-27 |
Family
ID=5274151
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB991097831A Expired - Lifetime CN1172981C (en) | 1999-07-15 | 1999-07-15 | Anti-hydrolysis organophosphoric deoxidant |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1172981C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102311618A (en) * | 2010-06-29 | 2012-01-11 | 金发科技股份有限公司 | Hydrolysis-resistant aliphatic-aromatic copolyester and preparation method thereof |
| CN106317453B (en) * | 2015-07-10 | 2018-10-26 | 奕益实业有限公司 | Liquid phosphorus-containing stabilizers and its preparation method |
| CN112063016A (en) * | 2020-11-16 | 2020-12-11 | 利安隆(天津)新材料科技有限公司 | Preparation method of long-acting phosphite ester antioxidant |
-
1999
- 1999-07-15 CN CNB991097831A patent/CN1172981C/en not_active Expired - Lifetime
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102311618A (en) * | 2010-06-29 | 2012-01-11 | 金发科技股份有限公司 | Hydrolysis-resistant aliphatic-aromatic copolyester and preparation method thereof |
| CN102311618B (en) * | 2010-06-29 | 2013-12-04 | 金发科技股份有限公司 | Hydrolysis-resistant aliphatic-aromatic copolyester and preparation method thereof |
| CN106317453B (en) * | 2015-07-10 | 2018-10-26 | 奕益实业有限公司 | Liquid phosphorus-containing stabilizers and its preparation method |
| CN112063016A (en) * | 2020-11-16 | 2020-12-11 | 利安隆(天津)新材料科技有限公司 | Preparation method of long-acting phosphite ester antioxidant |
| CN112063016B (en) * | 2020-11-16 | 2021-03-09 | 利安隆(天津)新材料科技有限公司 | Preparation method of long-acting phosphite ester antioxidant |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1172981C (en) | 2004-10-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0120115B1 (en) | Compositions based on a polysiloxane and an organo titanate and the use thereof in the preparation of water curable, silane modified alkylene-alkyl acrylate copolymers | |
| JP2015227464A (en) | Pigments treated with organo-phosphoric acids and their salts | |
| CN105121542B (en) | Opaque products vinyl chloride resin composition | |
| US20110021803A1 (en) | Purification and preparation of phosphorus-containing compounds | |
| CN101346312A (en) | Hydrotalcite-based compound particles, resin stabilizer using the same, halogen-containing resin composition and anion scavenger using the same | |
| JP5576893B2 (en) | Thermoplastic resin composition and method for producing the same | |
| CN1152909C (en) | Continuous process for producing organosilicon polymer | |
| EP1000121B1 (en) | Cross-linkable organopolysiloxane materials formed into elastomers by separating alcohols | |
| JP4106928B2 (en) | Flame retardant, method for producing the same, and flame retardant resin composition containing the same | |
| CN1907851A (en) | Organosol of silica and process for producing the same | |
| CN1172981C (en) | Anti-hydrolysis organophosphoric deoxidant | |
| JP5217226B2 (en) | Method for producing thermoplastic resin composition | |
| JP2003129056A (en) | Flame retardant having high effective surface area, production method therefor and flame-retardant resin composition containing the same | |
| CN1152910C (en) | Method for producing organosilicon polymer | |
| CN105968768A (en) | Phosphorus-containing composite flame retardant of core-shell structure and preparation method and application thereof | |
| TWI599604B (en) | Modified polymer materials and composite stabilizer composition | |
| JP2007270011A (en) | Laminar silicate compound and resin composition containing the laminar silicate compound | |
| US6362260B1 (en) | Phenol-free phosphite stabilizers | |
| US20030114559A1 (en) | Process for producing a styrenic resin composition | |
| DE19757308A1 (en) | Organopolysiloxane compositions which can be crosslinked with the elimination of alcohols to give elastomers | |
| US7041265B2 (en) | Alkaline earth metal-basic silicate particle | |
| US20020002222A1 (en) | Phosphorus-containing antioxidant stabilized against hydrolysis | |
| JP3370022B2 (en) | Hydrolysis-resistant organophosphorus antioxidant | |
| EP0400454A2 (en) | Stabilized phosphite compositions | |
| CN1768068A (en) | Phosphite reactions in the presence of metal soaps for liquid stabilisers |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CX01 | Expiry of patent term | ||
| CX01 | Expiry of patent term |
Granted publication date: 20041027 |