CN109400805A - One kind is with epoxy group liquid nitrile rubber and preparation method thereof - Google Patents

One kind is with epoxy group liquid nitrile rubber and preparation method thereof Download PDF

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Publication number
CN109400805A
CN109400805A CN201811240512.XA CN201811240512A CN109400805A CN 109400805 A CN109400805 A CN 109400805A CN 201811240512 A CN201811240512 A CN 201811240512A CN 109400805 A CN109400805 A CN 109400805A
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China
Prior art keywords
parts
epoxy group
nitrile rubber
liquid nitrile
group liquid
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CN201811240512.XA
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Chinese (zh)
Inventor
徐国亮
许桂
张典
汪贵玉
刘江
韩晓峰
张森
吕飚
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ANQING HUALAN TECHNOLOGY Co Ltd
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ANQING HUALAN TECHNOLOGY Co Ltd
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Priority to CN201811240512.XA priority Critical patent/CN109400805A/en
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F236/00Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F236/04Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F236/12Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with nitriles

Abstract

The invention discloses a kind of preparation methods with epoxy group liquid nitrile rubber, the following steps are included: synthesizing NBR latex by emulsion polymerization with butadiene, acrylonitrile, the unsaturated monomer with epoxy group first, then the NBR latex is obtained by cohesion, washing and drying and dehydrating and has epoxy group liquid nitrile rubber;In the synthesis NBR latex stage, in parts by weight, 25-40 parts of acrylonitrile, 55-74 parts of butadiene, it is any one or more of that molecular weight regulator is selected from 3- mercaptopropionic acid ethyl hexyl alcohol ester, isooctyl mercaptopropionate, four (3- mercaptopropionic acid) Ji Maosi alcohol esters or n-dodecyl mercaptan.Also disclose above method synthesis has epoxy group liquid nitrile rubber.The present invention has the advantages that going out to have epoxy group liquid nitrile rubber by one-step synthesis method, the technological process of production is simplified, progress resin solidification under cryogenic is realized and is modified, substantially increase modified effect, widened the application range of product.

Description

One kind is with epoxy group liquid nitrile rubber and preparation method thereof
Technical field
The present invention relates to the technical fields of liquid nitrile rubber, are more particularly to a kind of with epoxy group liquid butyronitrile rubber Glue and preparation method thereof.
Background technique
It is monomer that nitrile rubber, which is by butadiene and acrylonitrile, passes through a kind of polymer rubber made of emulsion polymerization Material makes its product have good heat-resisting, oil resistivity, is widely used in oil resistant rubber system since it contains itrile group structure Product, such as sealing ring, gasket, oil-resisting rubber hose field.Nitrile rubber according to its state difference, mainly have block nitrile rubber, Powdered nitrile rubber and liquid nitrile rubber, wherein liquid nitrile rubber, can due to good mobility and dispersibility Molecular level is other mixes to be formed with other liquid resins, possesses excellent toughening modifying effect, when mix with epoxy resin, and also Promote its peel strength, impact strength etc..
Liquid nitrile rubber refers generally to molecular weight 10000 hereinafter, itself being in the rubber of liquid condition, is broadly divided into common Liquid nitrile rubber without functional group, the random liquid nitrile rubber containing functional group and end group liquid nitrile rubber, functional group Usually there are carboxyl, amino, hydroxyl, sulfydryl, epoxy group etc., the corresponding polymerization methods of different functional groups structured liquids nitrile rubber Difference, wherein end group liquid nitrile rubber is largely polymerisation in solution, the liquid fourth without functional group or random functional group Nitrile rubber is usually to form by emulsion polymerization.Most commonly used carboxylic liquid nitrile rubber currently on the market, is answered extensively Plasticized modifier for resins such as epoxy resin, phenolic resin.As the toughener of epoxy resin, liquid butyronitrile is required first Rubber has good dissolubility in the epoxy, is well-dispersed in epoxy resin.In order to meet the above requirements, primarily now It is first to carry out mixing pre-polymerization with epoxy resin by carboxylic liquid nitrile rubber, so that carboxyl is first reacted with epoxy group, then In later period epoxy resin cure, guarantee to carry out curing reaction simultaneously, eventually form " island " structure, to have good Toughening effect.By this kind of method, epoxy resin is eventually made to reach ideal modified effect, but there is problems in that (1) reaction temperature of carboxyl and epoxy group is very high, generally higher than 100 DEG C reactions, this limits the application of epoxy resin System, because being much in 100 DEG C or less or room temperature curing;(2) time of the reaction is longer, generally at 2-6 hours;(3) in height The lower reaction of temperature, the crosslinking of molecule itself in order to prevent needs under closed nitrogen atmosphere, and suitable catalyst is added, It can guarantee that reaction is more complete.Therefore, epoxy terminated liquid nitrile rubber product is had on existing market, but the product is logical The liquid nitrile rubber with different functional groups is crossed, solvent and reagent is added, reaction obtains the said goods for a long time.Due to liquid Body nitrile rubber viscosity is larger, in subsequent reactions, after needing to be added a large amount of solvent dissolution, could react, subsequent also to return Solvent is received, process flow is more complicated.Therefore, by when liquid nitrile rubber synthesizes, epoxy group is just introduced, it can be to avoid Above-mentioned many difficulties and problems.
Summary of the invention
Technical problem to be solved by the present invention lies in provide a kind of simple production process, high conversion rate, at low cost, tool There are excellent toughening effect, the liquid nitrile rubber containing epoxy group of good caking property and resistance to low temperature and its preparation side Method.
The present invention is to solve above-mentioned technical problem by the following technical programs:
On the one hand, a kind of preparation method with epoxy group liquid nitrile rubber is provided, comprising the following steps: first with Butadiene, acrylonitrile, the unsaturated monomer with epoxy group synthesize NBR latex by emulsion polymerization, then by the nitrile rubber Cream obtains by cohesion, washing and drying and dehydrating and has epoxy group liquid nitrile rubber;The NBR latex stage is being synthesized, with Parts by weight meter, 25-40 parts of acrylonitrile, 55-74 parts of butadiene, molecular weight regulator are selected from 3- mercaptopropionic acid ethyl hexyl alcohol ester, mercapto The different monooctyl ester of base propionic acid, four (3- mercaptopropionic acid) Ji Maosi alcohol esters or n-dodecyl mercaptan are any one or more of.
Preferably, in the synthesis NBR latex stage, deionized water, emulsifier, electrolyte, reducing agent, molecule are successively put into Regulator, acrylonitrile, unsaturated monomer, initiator and butadiene are measured, 20-40 DEG C is warming up to, starts to react, when conversion ratio reaches When 30-40%, molecular weight regulator is added for the first time;When conversion ratio reaches 50-60%, molecular-weight adjusting is added for the second time Agent;When conversion ratio reaches 70-80%, molecular weight regulator is added for the third time, and the reaction was continued reaches 98% or more to conversion ratio When, stop reaction, terminator is added, synthesizes NBR latex.The molecular weight regulator put into for the first time and for the first time, second and the The molecular weight regulator added three times can be same substance, can also be different material.
Preferably, by weight, acrylonitrile 25-40 parts, 1-5 parts of unsaturated monomer, 55-74 parts of butadiene, emulsifier 2.0-4.0 parts, 0.3-1.0 parts of electrolyte, 4-8 parts of molecular weight regulator, 0.1-0.5 parts of reducing agent, 0.4-1.2 parts of initiator, 180-220 parts of deionized water adds 1-4 parts of molecular weight regulator for the first time, adds 1-4 parts of molecular weight regulator, for the second time 2-6 parts of molecular weight regulator are added three times.
Preferably, the unsaturated monomer is selected from glycidyl acrylate and/or glycidyl methacrylate;Institute Emulsifier is stated in disproportionated rosin acid potassium, neopelex, lauryl sodium sulfate, potassium stearate or potassium oleate It is any one or more;The electrolyte be selected from any one of potassium carbonate, potassium chloride, sodium carbonate, sodium bicarbonate or potassium phosphate or It is a variety of;It is any one or more of that the initiator is selected from ammonium persulfate, potassium peroxydisulfate or di-isopropylbenzene hydroperoxide;It is described to go back It is any one or more of that former agent is selected from sodium formaldehyde sulfoxylate, diethanol amine or triethanolamine.
Preferably, in NBR latex agglomeration phase, deionized water and flocculating agent are sequentially added, opens stirring, then slowly The NBR latex is added, is condensed into the slurries of white.
Preferably, by weight, 100 parts of NBR latex, 150-200 parts of deionized water, 2-6 parts of flocculating agent.
Preferably, the flocculating agent is selected from one of calcium chloride, magnesium sulfate, aluminum sulfate or aluminum aluminum sulfate or a variety of.
Preferably, the mode of the washing is hot water wash washing, and the mode of the drying and dehydrating is vacuum dehydration.
Preferably, the hot water temperature is 70-95 DEG C, and the drying temperature is 80-90 DEG C, the vacuum drying vacuum Degree is -0.07MPa--0.09MPa.
On the other hand, it also provides made of above-mentioned preparation method with epoxy group liquid nitrile rubber, epoxy should be had Moisture content < 1.0% in group liquid nitrile rubber.
The present invention has the advantage that epoxy group using one-step method polymerization reaction, is introduced liquid by (1) compared with prior art In body nitrile rubber molecular structure, synthesizes with epoxy group liquid nitrile rubber, improve properties of product, in downstream product When modified, production technology is simplified, is not required to obtain epoxy group by the reaction between subsequent different functional groups, when shortening Between, widen application field range;(2) in polymerization, it is used at present to replace to introduce other kinds of molecular weight regulator Tert-dodecylmercaotan reduces the stink in product, while being also beneficial to environmental protection;(3) pass through the conversion conditions in setting Under, secondary addition molecular weight regulator, can make molecular structure more uniform, while also preferably controlling molecular weight in three batches Size;(4) by using the mode that reducing agent is added, suitably reduction reaction temperature, be conducive to the molecular structure for controlling polymer, Promote polymerization reaction and improves final conversion ratio;(5) by using under high vacuum, cryogenic conditions remove glue in moisture, Drying temperature is effectively reduced, is avoided easy during drying and dehydrating under more than 100 DEG C hot conditions in oxygen-free environment Cause to be cross-linked to form gel, while the liquid nitrile rubber product color produced under this condition is shallower, is conducive to apply In colourless or light color article modification, application range is more extensive.
Specific embodiment
It elaborates below to the embodiment of the present invention, the present embodiment carries out under the premise of the technical scheme of the present invention Implement, the detailed implementation method and specific operation process are given, but protection scope of the present invention is not limited to following implementation Example.
Embodiment 1
(1) synthesis of NBR latex: first vacuumizing polymeric kettle, successively put into according to weight ratio 190 parts of deionized water, 3.0 parts of emulsifier disproportionated rosin acid potassium, 0.5 part of electrolyte potassium carbonate, 0.2 part of reducing agent sodium formaldehyde sulfoxylate, molecular weight regulator 3- mercapto 6 parts of base propionic acid ethyl hexyl alcohol ester, 29 parts of acrylonitrile, 3 parts of unsaturated monomer glycidyl acrylate, initiator ammonium persulfate 0.6 part, inflated with nitrogen vacuumize repeatedly twice, be added 68 parts of butadiene, open stirring, start to warm up to 20-40 DEG C;When polymerization is anti- When conversion ratio being answered to reach 30-40%, start to add 2 parts of alcohol ester of molecular weight regulator 3- mercaptopropionic acid ethyl hexyl for the first time;When poly- When conjunction reaction conversion ratio reaches 50-60%, start to add 2 parts of alcohol ester of molecular weight regulator 3- mercaptopropionic acid ethyl hexyl for the second time; When polymerization conversion reaches 70-80%, starts third time and add molecular weight regulator 3- mercaptopropionic acid ethyl hexyl alcohol ester 3 Part, the reaction was continued when reaching 98% or more to polymerisation conversion, stops reaction, terminator Sodium Dimethyldithiocarbamate is added, needed for finally obtaining NBR latex.Through detecting, polymerisation conversion 98.5%.
(2) 150 parts of deionized water, flocculating agent chlorine successively the cohesion of NBR latex: are added into condensing field according to weight ratio Change 4 parts of calcium, open stirring, then be slowly added to condensing field 100 parts of NBR latex of above-mentioned preparation, is condensed into the glue of white, Using washing and vacuum dehydration, finally obtain with epoxy group liquid nitrile rubber.After testing, technical indicator Are as follows: viscosity 22000cps, epoxy group content 0.25mmol/g, moisture 0.3%.
Embodiment 2
In the synthesis step of NBR latex, 200 parts of deionized water, 33 parts of acrylonitrile, butadiene 64 will be added in embodiment 1 Part, other process recipes are same as embodiment 1.Through detecting, polymerisation conversion 98.6%.
It is condensed into glue, washing and vacuum dehydration again, is finally obtained with epoxy group liquid nitrile rubber.Through Cross detection, technical indicator are as follows: viscosity 28000cps, epoxy group content 0.24mmol/g, moisture 0.4%.
Embodiment 3
In the synthesis step of NBR latex, 200 parts of deionized water, 40 parts of acrylonitrile, butadiene 57 will be added in embodiment 1 Part, other process recipes are same as embodiment 1.Through detecting, polymerisation conversion 98.8%.
It is condensed into glue, washing and vacuum dehydration again, is finally obtained with epoxy group liquid nitrile rubber.Through Cross detection, technical indicator are as follows: viscosity 38000cps, epoxy group content 0.26mmol/g, moisture 0.3%.
Embodiment 4
In the synthesis step of NBR latex, 200 parts of deionized water, 40 parts of acrylonitrile, butadiene 57 will be added in embodiment 1 Part, 8 parts of molecular weight regulator isooctyl mercaptopropionate, other process recipes are same as embodiment 1.Through detecting, polymerisation conversion is 98.8%.
It is condensed into glue, washing and vacuum dehydration again, is finally obtained with epoxy group liquid nitrile rubber.Through Cross detection, technical indicator are as follows: viscosity 35000cps, epoxy group content 0.23mmol/g, moisture 0.3%.
Embodiment 5
In the synthesis step of NBR latex, 200 parts of deionized water, 40 parts of acrylonitrile, butadiene 57 will be added in embodiment 1 Part, 8 parts of molecular weight regulator four (3- mercaptopropionic acid) Ji Maosi alcohol ester, to add molecular weight regulator mercaptopropionic acid for the first time different pungent 4 parts of ester adds 4 parts of molecular weight regulator four (3- mercaptopropionic acid) Ji Maosi alcohol ester for the second time, adds molecular-weight adjusting for the third time 6 parts of agent isooctyl mercaptopropionate, other process recipes are same as embodiment 1.Through detecting, polymerisation conversion 98.3%.
It is condensed into glue, washing and vacuum dehydration again, is finally obtained with epoxy group liquid nitrile rubber.Through Cross detection, technical indicator are as follows: viscosity 18000cps, epoxy group content 0.23mmol/g, moisture 0.5%.
Embodiment 6
By in embodiment 1 in the synthesis step of NBR latex, 4.5 parts of unsaturated monomer glycidyl methacrylate, 66.5 parts of butadiene, other process recipes are same as embodiment 1.Through detecting, polymerisation conversion 98.7%.
It is condensed into glue, washing and vacuum dehydration again, is finally obtained with epoxy group liquid nitrile rubber.Through Cross detection, technical indicator are as follows: viscosity 25000cps, epoxy group content 0.45mmol/g, moisture 0.4%.
Embodiment 7
By in embodiment 1 in the synthesis step of NBR latex, 4.0 parts of emulsifier neopelex, electrolyte carbon 0.6 part of sour sodium, other process recipes are same as embodiment 1.Through detecting, polymerisation conversion 99.0%.
It is condensed into glue, washing and vacuum dehydration again, is finally obtained with epoxy group liquid nitrile rubber.Through Cross detection, technical indicator are as follows: viscosity 26000cps, epoxy group content 0.25mmol/g, moisture 0.3%.
Embodiment 8
By in embodiment 1 in the synthesis step of NBR latex, 0.8 part of initiator di-isopropylbenzene hydroperoxide, reducing agent two 0.3 part of ethanol amine, other process recipes are same as embodiment 1.Through detecting, polymerisation conversion 99.2%.
It is condensed into glue, washing and vacuum dehydration again, is finally obtained with epoxy group liquid nitrile rubber.Through Cross detection, technical indicator are as follows: viscosity 19000cps, epoxy group content 0.24mmol/g, moisture 0.3%.
Embodiment 9
By in embodiment 1 in the synthesis step of NBR latex, 8 parts of molecular weight regulator n-dodecyl mercaptan, for the first time It adds 3 parts of molecular weight regulator n-dodecyl mercaptan, add molecular weight regulator four (3- mercaptopropionic acid) Ji Maosi for the second time 3 parts of alcohol ester adds 4 parts of molecular weight regulator n-dodecyl mercaptan for the third time, other process recipes are same as embodiment 1.Through examining It surveys, polymerisation conversion 98.5%.
It is condensed into glue, washing and vacuum dehydration again, is finally obtained with epoxy group liquid nitrile rubber.Through Cross detection, technical indicator are as follows: viscosity 12000cps, epoxy group content 0.23mmol/g, moisture 0.5%.
Embodiment 10
By in the synthesis step of NBR latex, 200 parts of deionized water, is gone back at 1.0 parts of initiator potassium persulfate in embodiment 1 0.4 part of former agent diethanol amine, other process recipes are same as embodiment 1.Through detecting, polymerisation conversion 98.9%.
It is condensed into glue, washing and vacuum dehydration again, is finally obtained with epoxy group liquid nitrile rubber.Through Cross detection, technical indicator are as follows: viscosity 14000cps, epoxy group content 0.25mmol/g, moisture 0.3%.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.

Claims (10)

1. a kind of preparation method with epoxy group liquid nitrile rubber, comprising the following steps: first with butadiene, propylene Nitrile, the unsaturated monomer with epoxy group synthesize NBR latex by emulsion polymerization, then agglomerate NBR latex process, Washing and drying and dehydrating obtain and have epoxy group liquid nitrile rubber;It is characterized by:
In the synthesis NBR latex stage, in parts by weight, 25-40 parts of acrylonitrile, 55-74 parts of butadiene, molecular weight regulator choosing From 3- mercaptopropionic acid ethyl hexyl alcohol ester, isooctyl mercaptopropionate, four (3- mercaptopropionic acid) Ji Maosi alcohol esters or dodecyl sulphur Alcohol is any one or more of.
2. the preparation method according to claim 1 with epoxy group liquid nitrile rubber, which is characterized in that synthesizing The NBR latex stage successively puts into deionized water, emulsifier, electrolyte, reducing agent, molecular weight regulator, acrylonitrile, unsaturation Monomer, initiator and butadiene, are warming up to 20-40 DEG C, start to react, and when conversion ratio reaches 30-40%, add for the first time point Son amount regulator;When conversion ratio reaches 50-60%, molecular weight regulator is added for the second time;When conversion ratio reaches 70-80% When, molecular weight regulator is added for the third time, the reaction was continued when reaching 98% or more to conversion ratio, stops reaction, Sodium Dimethyldithiocarbamate is added, Synthesize NBR latex.
3. the preparation method according to claim 2 with epoxy group liquid nitrile rubber, which is characterized in that by weight Part meter, 25-40 parts of acrylonitrile, 1-5 parts of unsaturated monomer, 55-74 parts of butadiene, 2.0-4.0 parts of emulsifier, electrolyte 0.3- 1.0 parts, 4-8 parts of molecular weight regulator, 0.1-0.5 parts of reducing agent, 0.4-1.2 parts of initiator, 180-220 parts of deionized water, Once 1-4 parts of molecular weight regulator is added, 1-4 parts of molecular weight regulator is added for the second time, adds molecular weight regulator for the third time 2-6 parts.
4. the preparation method according to claim 2 with epoxy group liquid nitrile rubber, which is characterized in that it is described not It is saturated monomer and is selected from glycidyl acrylate and/or glycidyl methacrylate;The emulsifier is selected from disproportionated rosin Sour potassium, neopelex, lauryl sodium sulfate, potassium stearate or potassium oleate are any one or more of;The electricity It is any one or more of selected from potassium carbonate, potassium chloride, sodium carbonate, sodium bicarbonate or potassium phosphate to solve matter;The initiator is selected from Ammonium persulfate, potassium peroxydisulfate or di-isopropylbenzene hydroperoxide are any one or more of;The reducing agent is selected from sodium formaldehyde sulfoxylate, diethyl Hydramine or triethanolamine are any one or more of.
5. the preparation method according to claim 1 with epoxy group liquid nitrile rubber, which is characterized in that in butyronitrile The emulsion condensation stage sequentially adds deionized water and flocculating agent, opens stirring, is then slowly added into the NBR latex, agglomerates At the slurries of white.
6. the preparation method according to claim 5 with epoxy group liquid nitrile rubber, which is characterized in that by weight Part meter, 100 parts of NBR latex, 150-200 parts of deionized water, 2-6 parts of flocculating agent.
7. the preparation method according to claim 5 with epoxy group liquid nitrile rubber, which is characterized in that described solidifying Poly- agent is selected from one of calcium chloride, magnesium sulfate, aluminum sulfate or aluminum aluminum sulfate or a variety of.
8. the preparation method according to claim 1 with epoxy group liquid nitrile rubber, which is characterized in that described to wash The mode washed is hot water wash washing, and the mode of the drying and dehydrating is vacuum dehydration.
9. the preparation method according to claim 8 with epoxy group liquid nitrile rubber, which is characterized in that the heat Coolant-temperature gage is 70-95 DEG C, and the drying temperature is 80-90 DEG C, and the vacuum drying vacuum degree is -0.07MPa-- 0.09MPa。
10. epoxy group liquid nitrile rubber is had made of preparation method according to any one of claim 1 to 9, It is characterized in that, described with moisture content < 1.0% in epoxy group liquid nitrile rubber.
CN201811240512.XA 2018-10-24 2018-10-24 One kind is with epoxy group liquid nitrile rubber and preparation method thereof Pending CN109400805A (en)

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CN113683959A (en) * 2021-10-27 2021-11-23 科顺防水科技股份有限公司 Two-component rubber asphalt waterproof coating composition and structure applying same
CN115322295A (en) * 2022-09-16 2022-11-11 安庆华兰科技有限公司 Random hydroxyl liquid nitrile rubber and preparation method and application thereof

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113683959A (en) * 2021-10-27 2021-11-23 科顺防水科技股份有限公司 Two-component rubber asphalt waterproof coating composition and structure applying same
CN115322295A (en) * 2022-09-16 2022-11-11 安庆华兰科技有限公司 Random hydroxyl liquid nitrile rubber and preparation method and application thereof
CN115322295B (en) * 2022-09-16 2024-02-13 安庆华兰科技有限公司 Random hydroxyl liquid nitrile rubber and preparation method and application thereof

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Application publication date: 20190301