CN105949510B - A kind of rubber product additive and preparation method thereof - Google Patents

A kind of rubber product additive and preparation method thereof Download PDF

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Publication number
CN105949510B
CN105949510B CN201610514515.2A CN201610514515A CN105949510B CN 105949510 B CN105949510 B CN 105949510B CN 201610514515 A CN201610514515 A CN 201610514515A CN 105949510 B CN105949510 B CN 105949510B
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binary
alcohol
phosphoric acid
metal oxide
rubber product
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CN105949510A (en
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陈思佳
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Fengcheng Friendship Chemistry Co., Ltd.
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Fengcheng Friendship Chemistry Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/49Phosphorus-containing compounds
    • C08K5/5398Phosphorus bound to sulfur
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07FACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02Phosphorus compounds
    • C07F9/06Phosphorus compounds without P—C bonds
    • C07F9/16Esters of thiophosphoric acids or thiophosphorous acids
    • C07F9/165Esters of thiophosphoric acids
    • C07F9/1651Esters of thiophosphoric acids with hydroxyalkyl compounds with further substituents on alkyl
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00Compositions of unspecified rubbers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Biochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)

Abstract

The present invention relates to a kind of rubber product additives, it is the derivative that sulphur phosphoric acid is made by raw material of the above alcohol of binary, phosphorus pentasulfide and bivalent metal oxide, the molar ratio of raw material is as follows in its production: the molar ratio of the above alcohol of binary and phosphorus pentasulfide is 1-4:1, the molar ratio 1:1-2 of bivalent metal oxide and sulphur phosphoric acid.The present invention also provides a kind of preparation methods of rubber product additive.The present invention using binary above alcohol substitution butanol as alkyl-thio-phosphate the born output of raw material come product, as the promotor and activating agent in compounding rubber, suction-operated of the white carbon black to auxiliary agent can not only be reduced, it is also environmentally friendly simultaneously, Carcinogenic Nitrosamines are not generated, the working environment of mixing action worker can be improved.

Description

A kind of rubber product additive and preparation method thereof
Technical field
The present invention relates to rubber production field, specifically a kind of existing active function has the rubber product of promotion functions to add again Add agent and preparation method thereof.
Background technique
Filling of the white carbon black as rubber product, all advantageous to wetland gripping power, low-rolling-resistance, present application is more next It is bigger, but white carbon black has stronger adsorptivity, can adsorb the auxiliary agent in rubber compounding, reduces its efficiency, increases making for auxiliary agent Dosage, so that production cost rises.
In addition, general promotor can generate nitrosamine carcinogenic substance in the mixing of rubber, compounding rubber work is seriously affected Physical and mental health, so the promotor substitution for thering is the promotor such as NOBS of many high risks not generated nitrosamine.Alkyl Thiophosphate and ester do not generate nitrosamine, Food and Drug Administration due to being free of secondary amine structure in its molecular structure (FDA) to it in the rubber of contact food using there is no limit, and the compatibility of such product and rubber is good, does not spit frost, Heated light does not generate xanthochromia, by the attention of user and likes now, especially in the rubber product with human contact, such as shoes It is widely used in industry, automobile industry.The product of present successful commercialization has: the promotor ZBPD of U.S. Fu Laikesi, chemical name Title is dibutyl sulfide for trbasic zinc phosphate, and the preparation process of ZBPD is:
4C4H9OH+P2S5----2(C4H9O)2PS2H+H2S
2(C4H9O)2PS2H+ZnO---[2(C4H9O)2PS2]2Zn+H2O
But dibutyl sulfide is promotor for trbasic zinc phosphate, the not effect of activating agent.
Based on this, the present invention is specifically proposed.
Summary of the invention
In order to solve above-mentioned problems of the prior art, the present invention provides a kind of rubber product additive, existing work Property agent function has accelerator function again, not only environmentally friendly, but also can be reduced auxiliary dosage, to reduce being produced into for rubber product This.
The technical scheme is that
A kind of rubber product additive, for using the above alcohol of binary, phosphorus pentasulfide and bivalent metal oxide as raw material The derivative of sulphur phosphoric acid is made, the preparation method of the derivative includes the following steps:
4R(OH)n+P2S5----2[(HO)n-1RO]2PS2H+H2S
2[(HO)n-1RO]2PS2H+MO---{[(HO)n-1RO]2PS2}2M+H2O
2[(HO)n-1OR]2PS2H----[(HO)n-1RO]2PS4P[(HO)n-1RO]2
Wherein, sulphur phosphoric acid is reacted by more than binary pure and mild phosphorus pentasulfide and is made, the above alcohol of binary and phosphorus pentasulfide Molar ratio is 3-4:1, and reaction temperature is at 60 degrees Celsius -90 degrees Celsius, and reaction humidity is 60% hereinafter, the moisture of the above alcohol of binary It is required that 0.2% hereinafter, adding phosphorus pentasulfide into the above alcohol of binary when preparing;
Wherein, sulfate-phosphate is made by sulphur phosphoric acid and reactive metal oxide, and bivalent metal oxide rubs with sulphur phosphoric acid You are than being 1:1.2-1.8, and at 30 degrees Celsius -100 degrees Celsius, metal oxide is added reaction temperature into sulphur phosphoric acid, metal oxygen Compound is added portionwise, to promote the abundant fully reacting of metal oxide.
Optionally, the above alcohol of the binary is single alcohol or mixed alcohol.
Optionally, the above alcohol of the binary is liquid alcohol or solid alcohol.
Further, the derivative has exposed hydroxyl.
Further, the derivative be the alkyl-thio-phosphate of hydroxyl or be hydroxyl alkylthio phosphoric acid Ester.
Further, the alkyl-thio-phosphate of the hydroxyl is zinc salt, amine salt, calcium salt, magnesium salts, sodium salt or sylvite.
The present invention also provides a kind of rubber product additive preparation methods, comprise the following steps that
4R(OH)n+P2S5----2[(HO)n-1RO]2PS2H+H2S
2[(HO)n-1RO]2PS2H+MO---{[(HO)n-1RO]2PS2}2M+H2O
2[(HO)n-1OR]2PS2H----[(HO)n-1RO]2PS4[(HO)n-1RO]2PS4P[(HOR)n-1O]2
Wherein, sulphur phosphoric acid is reacted by more than binary pure and mild phosphorus pentasulfide and is made, and reaction temperature is Celsius at 30 degree Celsius -90 Degree, reaction humidity is 80% hereinafter, the moisture content of the above alcohol of binary is required 0.2% hereinafter, by phosphorus pentasulfide toward two when preparation Add in the above alcohol of member;
Wherein, sulfate-phosphate is made by sulphur phosphoric acid and reactive metal oxide, and reaction temperature is Celsius at 30 degree Celsius -100 Degree, metal oxide are added into sulphur phosphoric acid, and metal oxide is added portionwise, to promote the abundant fully reacting of metal oxide.
Further, more than binary the temperature of pure and mild phosphorus pentasulfide reaction is 60 degrees Celsius -90 degrees Celsius, and humidity exists 60% or less.
Beneficial effects of the present invention: it is born using the above alcohol substitution butanol of binary as the raw material of alkyl-thio-phosphate The product that output is come can not only reduce white carbon black and make to the absorption of auxiliary agent as the promotor and activating agent in compounding rubber With, while it is also environmentally friendly, Carcinogenic Nitrosamines are not generated, the working environment of mixing action worker can be improved.
Specific embodiment
With reference to embodiments, a kind of rubber product additive of the present invention and preparation method thereof is further described.
Embodiment 1: rubber product additive of the invention, for the above alcohol of binary, phosphorus pentasulfide and divalent metal oxygen Compound is the derivative that sulphur phosphoric acid is made in raw material, and the molar ratio of raw material is as follows in production:
The molar ratio of the above alcohol of binary and phosphorus pentasulfide is 2-4:1,
The molar ratio 1:1-2 of bivalent metal oxide and sulphur phosphoric acid.
Preferably, the molar ratio of the above alcohol of binary and phosphorus pentasulfide is 3-4:1.
Preferably, the molar ratio 1:1.2-1.8 of bivalent metal oxide and sulphur phosphoric acid.
Wherein, sulphur phosphoric acid is reacted by more than binary pure and mild phosphorus pentasulfide and is made, and reaction temperature is Celsius at 30 degree Celsius -90 Degree, reaction humidity is 80% hereinafter, the moisture content of the above alcohol of binary is required 0.2% hereinafter, by phosphorus pentasulfide toward two when preparation Add in the above alcohol of member;
Wherein, sulfate-phosphate is made by sulphur phosphoric acid and reactive metal oxide, and reaction temperature is Celsius at 30 degree Celsius -100 Degree, metal oxide are added into sulphur phosphoric acid, and metal oxide is added portionwise, to promote the abundant fully reacting of metal oxide.
It prepares reaction process are as follows:
4HOC2H4OC2H4OH+P2S5----2(HOC2H4OC2H4O)2PS2H+H2S
2(HOC2H4OC2H4O)2PS2H+ZnO---[2(HOC2H4OC2H4O)2PS2]2Zn+H2O
2(HOC2H4OC2H4O)2PS2H-- oxidation -- (HOC2H4OC2H4O)2PS4P(HOC2H4OC2H4O)2
Specific practice is: in the 1000ml four-hole bottle stirred with thermometer, 0.2% or less 424.0 grams of water content are added Diethylene glycol (DEG), be added slowly with stirring 222.0 grams of phosphorus pentasulfide, control temperature at 30 degrees Celsius -90 degrees Celsius, control Humidity hereinafter, absorb hydrogen sulfide simultaneously, avoids hydrogen sulfide leakage from causing danger 80%.After reaction, sulphur phosphorus is obtained by filtration It is sour stand-by.
In the 1000ml four-hole bottle stirred with thermometer, the sulphur phosphoric acid of obtained 490.0 grams of intermediate products above is added, Control reaction temperature at 30 degrees Celsius -100 degrees Celsius, be added with stirring 75.0 grams of zinc oxide, be dehydrated, filter hydroxyl production Product.
Embodiment 2: making step is identical with embodiment 1, only controls the temperature of the pure and mild phosphorus pentasulfide reaction of binary or more Degree is 60 degrees Celsius -90 degrees Celsius, and humidity is below 60%.
The formula and dosage of embodiment 3 and embodiment 4, as shown in the table respectively:
The step of making step of embodiment 3 and embodiment 4 is with embodiment 1 and embodiment 2 are identical, and different is only to match Side and dosage.
Test result is as follows shown in table:
It should be noted that in the above-described embodiment, the above alcohol of binary can be single alcohol, be also possible to mixed alcohol; It can be liquid alcohol, can also be solid alcohol, best solid alcohol is substantially dissolved in liquid alcohol or more than solid alcohol fusing point.
Final obtained product has exposed hydroxyl.
Final obtained product is the alkyl-thio-phosphate of hydroxyl, can be zinc salt, amine salt, calcium salt, magnesium salts, sodium salt Or sylvite etc..
Final obtained product may be the alkylphosphonothioate of hydroxyl.
More than binary pure and mild phosphorus pentasulfide reaction, reaction temperature is spent at 30 degree -100, preferably in 60-90 degree, if warm Spend it is low easily cause do not react early period, once reaction starting reaction it is uncontrollable, reaction temperature sharply increases, and hydrogen sulfide is easily caused to let out Leakage;If the high side reaction of temperature increases, product is decomposed.Reaction humidity is 80% hereinafter, preferably below 60%.Humidity height can promote Decompose phosphorus pentasulfide, products obtained therefrom is impure.The moisture content of the above alcohol of binary is required 0.2% hereinafter, due to phosphorus pentasulfide Water decomposition is met, moisture content height promotes phosphorus pentasulfide to resolve into phosphoric acid.
It should be noted that the R in reaction process represents alkyl, and the alkyl containing oxygen element, element sulphur, usually second Base, ethyl ether, propyl.The typical above alcohol of binary is ethylene glycol, diethylene glycol (DEG), glycerol, trimethylolpropane, etc..
The above content is combining, specific preferred embodiment is made for the present invention to illustrate the specific reality, and it cannot be said that of the invention The mode of applying is only limitted to this, for those of ordinary skill in the art to which the present invention belongs, is not departing from present inventive concept Under the premise of, several simple deductions and replacement can also be made, all will be regarded as belonging to claims institute of the invention submitted really Fixed protection scope.

Claims (5)

1. a kind of rubber product additive, it is characterised in that: it is with the oxidation of the above alcohol of binary, phosphorus pentasulfide and divalent metal Object be raw material be made sulphur phosphoric acid derivative, the derivative be the alkyl-thio-phosphate of hydroxyl or be hydroxyl alkyl The preparation method of thiophosphate, the derivative includes the following steps:
4R(OH)n+P2S5----2[(HO)n-1RO]2PS2H+H2S
2[(HO)n-1RO]2PS2H+MO----{[(HO)n-1RO]2PS2}2M+H2O
2[(HO)n-1OR]2PS2H----[(HO)n-1RO]2PS4P[(HO)n-1RO]2
Wherein, sulphur phosphoric acid is reacted by more than binary pure and mild phosphorus pentasulfide and is made, mole of the binary above alcohol and phosphorus pentasulfide Than for 3-4:1, reaction temperature is at 60 degrees Celsius -90 degrees Celsius, and reaction humidity is 60% hereinafter, the moisture requirement of the above alcohol of binary 0.2% hereinafter, adding phosphorus pentasulfide into the above alcohol of binary when preparing;
Wherein, sulfate-phosphate is made by sulphur phosphoric acid and reactive metal oxide, the molar ratio of bivalent metal oxide and sulphur phosphoric acid For 1:1.2-1.8, reaction temperature is at 30 degrees Celsius -100 degrees Celsius, and metal oxide is added into sulphur phosphoric acid, metal oxide It is added portionwise, to promote the abundant fully reacting of metal oxide.
2. rubber product additive as described in claim 1, it is characterised in that: the above alcohol of binary is single alcohol or mixing Alcohol.
3. rubber product additive as described in claim 1, it is characterised in that: the above alcohol of binary is liquid alcohol or solid Alcohol.
4. rubber product additive as described in claim 1, it is characterised in that: the derivative has exposed hydroxyl.
5. rubber product additive as described in claim 1, it is characterised in that: the alkyl-thio-phosphate of the hydroxyl is Zinc salt, ammonium salt, calcium salt, magnesium salts, sodium salt or sylvite.
CN201610514515.2A 2016-06-30 2016-06-30 A kind of rubber product additive and preparation method thereof Active CN105949510B (en)

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US3442804A (en) * 1967-01-19 1969-05-06 Lubrizol Corp Lubricating composition containing a phosphorodithioate inhibitor
EP2125839A4 (en) * 2007-01-31 2012-05-02 Vanderbilt Co R T Dithiophosphate composition and utility in rubber
CN103497357A (en) * 2013-10-10 2014-01-08 张义纲 Modified carbon black and preparation method thereof
CN103951698B (en) * 2014-05-09 2015-12-30 中国化工株洲橡胶研究设计院有限公司 A kind of O, O '-diene aerofloat and preparation method thereof

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