CN108912430A - A kind of chlorinated rubber and preparation method and purposes of nanometer additive and Sodium Allyl Sulfonate modified synergic - Google Patents
A kind of chlorinated rubber and preparation method and purposes of nanometer additive and Sodium Allyl Sulfonate modified synergic Download PDFInfo
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- CN108912430A CN108912430A CN201810814553.9A CN201810814553A CN108912430A CN 108912430 A CN108912430 A CN 108912430A CN 201810814553 A CN201810814553 A CN 201810814553A CN 108912430 A CN108912430 A CN 108912430A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/12—Incorporating halogen atoms into the molecule
- C08C19/14—Incorporating halogen atoms into the molecule by reaction with halogens
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L15/00—Compositions of rubber derivatives
- C08L15/02—Rubber derivatives containing halogen
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3009—Sulfides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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Abstract
The invention discloses a kind of nanometer additive and the chlorinated rubber of Sodium Allyl Sulfonate modified synergic and preparation method thereof, the nanometer additive is preferably nano tungsten disulfide.The chlorinated rubber good fluidity being prepared, and chlorinated rubber surface viscosity is strong, it is good with other polymers compatibility.Reaction overall process of the invention is completed under the aqueous-phase suspending state of the same reaction kettle, is not polluted to surrounding enviroment, and the reaction time is short, easy to operate, is easily converted into large-scale production, economic benefits.
Description
Technical field
The present invention relates to field of polymer chemical industry, and in particular to a kind of nano tungsten disulfide and Sodium Allyl Sulfonate collaboration change
The chlorinated rubber of property, preparation method and the usage.
Background technique
Chlorinated rubber is the derivative production of rubber obtained after chlorination modified by natural emulsion or natural rubber or synthetic rubber
Product are widely used in the fields such as ink, coating and adhesive.Before, chlorinated rubber is all to carry out chlorination reaction simultaneously with solvent method
Production, since solvent method is at high cost, and it is some as carbon tetrachloride equal solvent is harmful to the person and volatile matter pollutes environment
With residual solvent in product and use way it is restricted the defects of.Currently, the research that Aqueous phase prepares chlorinated rubber achieves centainly
Progress, many patent documents such as CN1667000A and CN101260168A disclose the research that Aqueous phase prepares chlorinated rubber
Achievement, but the defect of these methods is that operation is more complicated, and does not flow especially to the chlorinated rubber main performance of preparation
Dynamic property and viscosity and compatibility do any verifying.
Under normal conditions, by Aqueous phase prepare chlorinated rubber be it is powdered, then chlorinated rubber can be applied to paint,
The every field such as coating, adhesive.Therefore, the mobility of chlorinated rubber powder is to measure an important parameter of product.With
The application range of chlorinated rubber constantly expands, and more areas put forward new requirements chlorinated rubber, such as improves chlorinated rubber table
Face viscosity improves itself and the compatibility of other polymers etc..Patent document CN102358762A and non-patent literature " maleic anhydride
The synthesis of modified chlorinated polyethylene and adhesive property are studied, and are talked and are known macro etc., China's bonding academic discuss and product introduction meeting,
1998:5-8 " proposes improved method to the cementability of haloflex, but defect is that preparation process is more complex, and improves
The chlorinity of chlorinated polymeric is difficult to control and improves in the process.
In order to overcome the drawbacks of the prior art, missing of the prior art in terms of properties of product verifying is made up, the present invention mentions
For a kind of chlorinated rubber and preparation method thereof through nano tungsten disulfide and Sodium Allyl Sulfonate modified synergic, the reaction is single
With regard to achievable, easy to operate, high production efficiency, moreover it is possible to production cost be effectively reduced in reaction kettle.Chlorination prepared by the present invention
Rubber good fluidity, viscosity is big, good with other polymers compatibility.
Summary of the invention
It is an object of the present invention to provide the chlorination rubbers of a kind of nano tungsten disulfide and Sodium Allyl Sulfonate modified synergic
Glue and preparation method thereof, the chlorinated rubber good fluidity, surface viscosity is strong, good with other polymers compatibility, and should
Operation is simple, high production efficiency；The present invention, which a further object is, provides a kind of nano tungsten disulfide and Sodium Allyl Sulfonate
The purposes of the chlorinated rubber of modified synergic.
The purpose of the present invention is what is be achieved through the following technical solutions：
A kind of chlorinated rubber, according to the mass fraction, preparing raw material includes：100-130 parts of natural rubber, emulsifier 0.5-
3 parts, 0.1-0.2 parts of dispersing agent, 0.1-3 parts of defoaming agent, 0.2-3 parts of nanometer additive, 0.1-1 parts of Sodium Allyl Sulfonate, initiation
0.1-1 parts of agent, wherein nano tungsten disulfide and the mass ratio of Sodium Allyl Sulfonate are 1:1-1:5.
Preferably, the raw material for preparing of the chlorinated rubber includes：100-110 parts of natural rubber, divides 0.5-2 parts of emulsifier
0.1-0.15 parts of powder, 0.1-2 parts of defoaming agent, 0.2-1 parts of nanometer additive, 0.1-0.6 parts of Sodium Allyl Sulfonate, initiator
0.1-0.6 parts, wherein nano tungsten disulfide and the mass ratio of Sodium Allyl Sulfonate are 1:1-1:4.
The nanometer additive is selected from：Nano tungsten disulfide, nano molybdenum disulfide, nanometer tungsten hexachloride, nanometer hexafluoro antimony
Sour sodium.
Preferably, the nanometer additive is selected from：Nano tungsten disulfide.
In a preferred embodiment of the invention, the raw material for preparing of the chlorinated rubber includes：100 parts of natural rubber, cream
1 part of agent, 0.1 part of dispersing agent, 1 part of defoaming agent, 0.4 part of nano tungsten disulfide, 0.4 part of Sodium Allyl Sulfonate, initiator 0.3
Part, nano tungsten disulfide and the mass ratio of Sodium Allyl Sulfonate are 1 at this time:1.
The emulsifier is selected from：NONYL PHENOL POLYOXYETHYLENE, polyoxyethylene aliphatic alcohol ether, polyoxyethylene sorbitol oleic acid
Ester, polyoxyethylene nonylphenol ether, alkyl phenolic group polyoxyethylene ether, castor oil-polyoxyethylene ether, C12—C14Alkanoic acid diethanol amine
One or more of combination.
Preferably, the emulsifier is selected from：Alkyl phenolic group polyoxyethylene ether, castor oil-polyoxyethylene ether, polyoxyethylene
The combination of one or more of fatty alcohol ether.
In a preferred embodiment of the invention, the emulsifier is selected from：Castor oil-polyoxyethylene ether.
The dispersing agent is selected from：Alkyl trimethyl ammonium chloride, myristyl benzyl dimethyl ammonium chloride, etradecyldimethylamine
Base allyl ammonium chloride, stearyl dimethyl benzyl ammonium chloride, zephiran, Cocoalkyl trimethyl chlorine
Change the combination of one or more of ammonium, alkyl trimethyl sulfate methyl ammonium.
Preferably, the dispersing agent is selected from：Alkyl trimethyl ammonium chloride, stearyl dimethyl benzyl ammonium chloride, cocounut oil
The combination of one or more of alkyl trimethyl ammonium chloride, alkyl trimethyl sulfate methyl ammonium.
In a preferred embodiment of the invention, the dispersing agent is selected from：Alkyl trimethyl ammonium chloride.
Defoaming agent is selected from：The fatty acid ester compounded object of silicone emulsion, dimethyl silicone polymer, higher alcohols, polyoxyethylene polyoxy
Propyl alcohol amidogen ether, polypropylene glycerol aether, polyoxyethylene polyoxypropylene glycerin ether.
Preferably, the defoaming agent is selected from：One or both of silicone emulsion, dimethyl silicone polymer.
In a preferred embodiment of the invention, the defoaming agent is selected from：Dimethyl silicone polymer.
The initiator is selected from：Peroxidation sulfuric acid potassium, sodium peroxydisulfate, dilauroyl peroxide, azodiisobutyronitrile,
The combination of one or more of dibenzoyl peroxide, benzoyl peroxide.
Preferably, the initiator is selected from：Peroxidation sulfuric acid potassium, dilauroyl peroxide, azodiisobutyronitrile, peroxidating
The combination of one or more of dibenzoyl.
In a preferred embodiment of the invention, the initiator is selected from：Dilauroyl peroxide.
A kind of preparation method of chlorinated rubber, includes the following steps：
(1) it by natural rubber after plasticating, dissolves by heating；
(2) Sodium Allyl Sulfonate, emulsifier, dispersing agent and defoaming agent is added, quickly stirs, adds initiator；
(3) it is passed through nitrogen discharge air into reaction system, above-mentioned reaction system is slowly heated up, is stirred simultaneously,
It is slowly introducing chlorine, the nanometer additive of half quality is added when temperature rises to 45-50 DEG C, 50 DEG C of maintenance is until chlorine is passed through
Amount reaches 40% or more；Continue to heat up, the nanometer additive of remaining half quality is added when temperature rises to 95-100 DEG C,
Being passed through for chlorine is completed before 150 DEG C, reaction was completed, leads to chlorine speed control in 35-45m3/h；
(4) regulator is added, is passed through oxygen and removes remaining chlorine, keep the temperature 1-1.5h；
(5) suspension is washed, depickling, filtering, drying, obtains chlorinated rubber powder.
Preferably, the solvent in the step (1) is selected from：The mixed solution of one or both of chloroform, tetrachloromethane；
Preferably, the mass fraction of solvent is 300-500 parts in the step (1).
Preferably, it is 40m that chlorine speed is led in the step (3)3/ h, the amount and ratio that each temperature section is passed through chlorine are through counting
It is controlled after calculation by measure monitor.
Preferably, regulator is n- dodecyl mereaptan in the step (4).
Preferably, depickling handles selection and is adjusted to neutrality with sodium bicarbonate in the step (5)；The drying mode is selected from：
One of spray drying, vacuum drying, freeze-drying, near-infrared drying and microwave drying；More preferably it is dried in vacuo, it is dry
Temperature is 30-50 DEG C.
Chlorinated rubber of the present invention is preparing the purposes in ink, paint, coating or adhesive.
Preferably, the chlorinated rubber is preparing the purposes in adhesive.
A kind of adhesive, the adhesive include chlorinated rubber of the present invention.
Preferably, the adhesive further includes modified resin, thixotropic agent, filler, preservative, plasticizer.
In the present invention, the mobility of chlorinated rubber powder is indicated with angle of repose and bulk density.
(angle of repose) refers in gravitational field at angle of repose, the free inclined-plane of powder stack layer and horizontal plane institute
The maximum angular of formation.Angle of repose is smaller, and frictional force is smaller, and mobility is better, it is considered that good fluidity when θ≤30 degree, θ≤40
It can satisfy the need for liquidity in production process when spending.In the present invention, the measurement at angle of repose is selected from injection method, i.e., by powder
It is slowly added into above funnel, the material leaked out from funnel bottom forms the inclination angle of coniform accumulation body in the horizontal plane.
Bulk density refers to density of the powder in certain container when the occupied state of (being as far as possible quiet stable state).
This numerical value also represents the filling physical property of powder, can indirectly indicate the adhesive force and mobility of powder.In order to reduce measurement
Error measures bulk density in the present invention and uses unified pods.
Medium viscosity of the present invention is 20% chlorinated rubber toluene solution with capillary viscometer, tests and obtains at 25 DEG C.
Compatibility of the present invention is to mix chlorinated rubber solution with other polymers solution, observes the clear of mixed liquor
Bright degree indicates compatibility with this.The other polymers include：Phenol-formaldehyde resin modified, neoprene, terpene modified resin,
The common polymer of the adhesive areas such as superchlorinated polyvinyl chloride resin.
Chlorinated rubber chlorinty prepared by the present invention is up to 60~70%, good fluidity, and chlorinated rubber surface viscosity
By force, good with other polymers compatibility, it is created more just for chlorinated rubber in the application that each field especially prepares adhesive area
The condition of benefit.Reaction overall process of the invention is completed under the aqueous-phase suspending state of the same reaction kettle, not to surrounding enviroment
It polluting, the reaction time is short, and it is easy to operate, easily it is converted into large-scale production, economic benefits.
Specific embodiment
The invention will be further described by the following examples, for embodiment, be real in scale trial production
Border operates the example being verified.The variation that those skilled in the art make on the basis of the present invention, without departing from institute of the present invention
The range of protection.Embodiments discussed below only makes an explanation to the present invention, not restricts to the present invention.
The preparation of 1 chlorinated rubber 1 of embodiment
First 100 parts of natural rubber are added 200 parts of chloroform after plasticating, dissolve by heating, add Sodium Allyl Sulfonate 0.4
Part, emulsifier castor oil -1 part of polyoxyethylene ether, 0.1 part of dispersing agent alkyl trimethyl ammonium chloride, defoaming agent polydimethylsiloxanes
1 part of alkane, quickly stirring mixes well it, is added 0.3 part of initiator dilauroyl peroxide.Nitrogen is passed through into reaction system will
Air discharge, heating reaction system make it slowly heat up, and stirring while is slowly introducing chlorine, the addition when temperature rises to 50 DEG C
0.2 part of nano tungsten disulfide, 50 DEG C of maintenance is until chlorine intake reaches 40%；Continue to heat up, again when temperature rises to 100 DEG C
0.2 part of nano tungsten disulfide is added, being passed through for chlorine is completed before 150 DEG C, reaction was completed, and the logical chlorine speed of whole process is 40m3/
h.Appropriate n- dodecyl mereaptan is added, is passed through oxygen and removes remaining chlorine, keep the temperature 1.5h；Suspension is washed, uses carbonic acid
Suspension is adjusted to neutral, filtering, vacuum drying by hydrogen sodium, obtains faint yellow chlorinated rubber powder.
The chlorinated rubber chlorinty 70% being prepared, angle of repose are 25 degree, bulk density 0.50g/ml, and viscosity is
40mPas, it is excellent with the compatibility of other polymers, it is expressed as ★ ★ ★ ★ ★ ★.
The preparation of 2 chlorinated rubber 2 of embodiment
First 100 parts of natural rubber are added 200 parts of chloroform after plasticating, dissolve by heating, add emulsifier castor oil-
1 part of polyoxyethylene ether, 0.1 part of dispersing agent alkyl trimethyl ammonium chloride, 1 part of defoaming agent dimethyl silicone polymer, quickly stirring makes
It is mixed well, and is added 0.3 part of initiator dilauroyl peroxide.It is passed through nitrogen into reaction system air is discharged, heating is anti-
Answer system that it is made slowly to heat up, stirring while is slowly introducing chlorine, and 0.2 part of nanometer curing is added when temperature rises to 50 DEG C
Molybdenum, 50 DEG C of maintenance is until chlorine intake reaches 40%；Continue to heat up, 0.2 part of nanometer two is added when temperature rises to 100 DEG C
Molybdenum sulfide completes being passed through for chlorine before 150 DEG C, and reaction was completed, and the logical chlorine speed of whole process is 40m3/h.It is added appropriate positive 12
Mercaptan is passed through oxygen and removes remaining chlorine, keeps the temperature 1.5h；Suspension is washed, is adjusted to suspension with sodium bicarbonate
Neutral, filtering, vacuum drying, obtain white chlorinated rubber powder.
The chlorinated rubber chlorinty 60% being prepared, angle of repose are 49 degree, bulk density 0.90g/ml, and viscosity is
5mPas, it is poor with the compatibility of other polymers, it is expressed as ★.
The preparation of 3 chlorinated rubber 3 of embodiment
First 100 parts of natural rubber are added 200 parts of chloroform after plasticating, dissolve by heating, add emulsifier castor oil-
1 part of polyoxyethylene ether, 0.1 part of dispersing agent alkyl trimethyl ammonium chloride, 1 part of defoaming agent dimethyl silicone polymer, quickly stirring makes
It is mixed well, and is added 0.3 part of initiator dilauroyl peroxide.It is passed through nitrogen into reaction system air is discharged, heating is anti-
Answer system that it is made slowly to heat up, stirring while is slowly introducing chlorine, and 0.2 part of nanometer curing is added when temperature rises to 50 DEG C
Tungsten, 50 DEG C of maintenance is until chlorine intake reaches 40%；Continue to heat up, 0.2 part of nanometer two is added when temperature rises to 100 DEG C
Tungsten sulfide completes being passed through for chlorine before 150 DEG C, and reaction was completed, and the logical chlorine speed of whole process is 40m3/h.It is added appropriate positive 12
Mercaptan is passed through oxygen and removes remaining chlorine, keeps the temperature 1.5h；Suspension is washed, is adjusted to suspension with sodium bicarbonate
Neutral, filtering, vacuum drying, obtain faint yellow chlorinated rubber powder.
The chlorinated rubber chlorinty 68% being prepared, angle of repose are 33 degree, bulk density 0.67g/ml, and viscosity is
21mPas, it is general with the compatibility of other polymers, it is expressed as ★ ★ ★.
The preparation of 4 chlorinated rubber 4 of embodiment
First 100 parts of natural rubber are added 200 parts of chloroform after plasticating, dissolve by heating, add Sodium Allyl Sulfonate 0.4
Part, emulsifier castor oil -1 part of polyoxyethylene ether, 0.1 part of dispersing agent alkyl trimethyl ammonium chloride, defoaming agent polydimethylsiloxanes
1 part of alkane, quickly stirring mixes well it, is added 0.3 part of initiator dilauroyl peroxide.Nitrogen is passed through into reaction system will
Air discharge, heating reaction system make it slowly heat up, and stirring while is slowly introducing chlorine, the addition when temperature rises to 50 DEG C
0.2 part of nano molybdenum disulfide, 50 DEG C of maintenance is until chlorine intake reaches 40%；Continue to heat up, again when temperature rises to 100 DEG C
0.2 part of nano molybdenum disulfide is added, being passed through for chlorine is completed before 150 DEG C, reaction was completed, and the logical chlorine speed of whole process is 40m3/
h.Appropriate n- dodecyl mereaptan is added, is passed through oxygen and removes remaining chlorine, keep the temperature 1.5h；Suspension is washed, uses carbonic acid
Suspension is adjusted to neutral, filtering, vacuum drying by hydrogen sodium, obtains white chlorinated rubber powder.
The chlorinated rubber chlorinty 70% being prepared, angle of repose are 40 degree, bulk density 0.83g/ml, and viscosity is
22mPas, it is general with the compatibility of other polymers, it is expressed as ★ ★.
5 comparative example of embodiment
Control group：According to the preparation method system of the modified chlorinated rubber of graphene disclosed in patent document CN104817743A
Standby to obtain control chlorinated rubber, chlorinty 67%, angle of repose is 40 degree, bulk density 0.78g/ml, viscosity 26mPas,
It is preferable with the compatibility of other polymers, it is expressed as ★ ★ ★.
Experimental group：The chlorinated rubber 1-4 of embodiment 1-4 preparation.
The performance parameter measured is compared, as shown in the table：
1 chlorinated rubber performance parameter of table compares
| Chlorinty | Angle of repose (degree) | Bulk density (g/ml) | Viscosity (mPas) | Compatibility | |
| Chlorinated rubber 1 | 70% | 25 | 0.50 | 40 | ★★★★★★ |
| Chlorinated rubber 2 | 60% | 49 | 0.90 | 5 | ★ |
| Chlorinated rubber 3 | 68% | 33 | 0.67 | 21 | ★★★ |
| Chlorinated rubber 4 | 70% | 40 | 0.83 | 22 | ★★ |
| Control group | 67% | 40 | 0.78 | 26 | ★★★ |
According to correlation data as can be seen that being prepared when nano tungsten disulfide and Sodium Allyl Sulfonate are added simultaneously
Chlorinated rubber chlorinty highest, angle of repose and bulk density are all smaller, illustrate chlorinated rubber good fluidity；Viscosity is big, with other
Polymer miscibility is good, illustrates that chlorinated rubber surface viscosity is effectively improved, and compatibility improves, and is it in every field spy
Be not adhesive area application made good place mat.
Embodiment 6 screens nano tungsten disulfide and Sodium Allyl Sulfonate optimum proportioning
The preparation method and raw material of chlorinated rubber are same as Example 1, and difference is only that nano tungsten disulfide and allyl
The mass ratio of base sodium sulfonate is different.
Chlorinated rubber 1：0.4 part of nano tungsten disulfide, 0.4 part of Sodium Allyl Sulfonate, the two mass ratio is 1:1.
Chlorinated rubber 5：0.2 part of nano tungsten disulfide, 0.4 part of Sodium Allyl Sulfonate, the two mass ratio is 1:2.
Chlorinated rubber 6：0.4 part of nano tungsten disulfide, 1.6 parts of Sodium Allyl Sulfonate, the two mass ratio is 1:4.
Chlorinated rubber 7：0.4 part of nano tungsten disulfide, 4 parts of Sodium Allyl Sulfonate, the two mass ratio is 1:10.
Chlorinated rubber 8：1 part of nano tungsten disulfide, 0.4 part of Sodium Allyl Sulfonate, the two mass ratio is 2.5:1.
The performance parameter measured is compared, as shown in the table：
2 chlorinated rubber performance parameter of table compares
| Chlorinty | Angle of repose (degree) | Bulk density (g/ml) | Viscosity (mPas) | Compatibility | |
| Chlorinated rubber 1 | 70% | 25 | 0.50 | 40 | ★★★★★★ |
| Chlorinated rubber 5 | 67% | 29 | 0.58 | 33 | ★★★★★★ |
| Chlorinated rubber 6 | 65% | 33 | 0.63 | 34 | ★★★★ |
| Chlorinated rubber 7 | 64% | 39 | 0.70 | 30 | ★★★ |
| Chlorinated rubber 8 | 63% | 40 | 0.74 | 31 | ★★★ |
According to correlation data we can see that：When nanometer disulphide and Sodium Allyl Sulfonate are used in combination, preparation
Obtained chlorinated rubber mobility parameter and viscosity and compatibility is good.Preferably, the nano tungsten disulfide and allyl
Base sodium sulfonate mass ratio is 1:1-1:4, most preferably, when 0.4 part of nano tungsten disulfide, 0.4 part of Sodium Allyl Sulfonate, the two matter
Amount is than being 1:When 1, various performance parameters are best.
The adhesive comparative example that embodiment 7 is prepared by chlorinated rubber
Adhesive 1：1 15 parts of chlorinated rubber, 10 parts of phenol-formaldehyde resin modified, 2 parts of extra light calcined magnesia, 0.2 part of hexamethylene,
1 part of ethyl acetate, environmentally friendly solvent oily 2 parts, 0.1 part of antioxidant BHT, above-mentioned substance are sufficiently mixed, high-speed stirred 6h, temperature
40 DEG C of degree, until becoming thick liquid.
Adhesive 2：2 15 parts of chlorinated rubber, 10 parts of phenol-formaldehyde resin modified, 2 parts of extra light calcined magnesia, 0.2 part of hexamethylene,
1 part of ethyl acetate, environmentally friendly solvent oily 2 parts, 0.1 part of antioxidant BHT, above-mentioned substance are sufficiently mixed, high-speed stirred 6h, temperature
40 DEG C of degree, until becoming thick liquid.
Adhesive 3：3 15 parts of chlorinated rubber, 10 parts of phenol-formaldehyde resin modified, 2 parts of extra light calcined magnesia, 0.2 part of hexamethylene,
1 part of ethyl acetate, environmentally friendly solvent oily 2 parts, 0.1 part of antioxidant BHT, above-mentioned substance are sufficiently mixed, high-speed stirred 6h, temperature
40 DEG C of degree, until becoming thick liquid.
Adhesive 4：4 15 parts of chlorinated rubber, 10 parts of phenol-formaldehyde resin modified, 2 parts of extra light calcined magnesia, 0.2 part of hexamethylene,
1 part of ethyl acetate, environmentally friendly solvent oily 2 parts, 0.1 part of antioxidant BHT, above-mentioned substance are sufficiently mixed, high-speed stirred 6h, temperature
40 DEG C of degree, until becoming thick liquid.
Adhesive 5：5 15 parts of chlorinated rubber, 10 parts of phenol-formaldehyde resin modified, 2 parts of extra light calcined magnesia, 0.2 part of hexamethylene,
1 part of ethyl acetate, environmentally friendly solvent oily 2 parts, 0.1 part of antioxidant BHT, above-mentioned substance are sufficiently mixed, high-speed stirred 6h, temperature
40 DEG C of degree, until becoming thick liquid.
Viscosity, initial adhesive strength and the clarity of the adhesive 1-5 of above method preparation are compared, the viscosity is with rotatably
Viscosity meter.Correlation data is as shown in the table.
3 Adhensive performance comparing result of table
| Viscosity (mPas) | Initial adhesive strength (MPa) | Clarity | |
| Adhesive 1 | 680 | 1.1 | Liquid is uniform clear and bright |
| Adhesive 2 | 452 | 0.5 | Naked eyes visible white is cotton-shaped |
| Adhesive 3 | 557 | 0.7 | Clarity is preferable |
| Adhesive 4 | 539 | 0.7 | Clarity is preferable |
| Adhesive 5 | 603 | 0.9 | Clarity is good |
The adhesive viscosity that it can be seen from the above correlation data prepared by chlorinated rubber 1 is maximum, and initial adhesive strength highest,
The adhesive being prepared is uniform clear and bright.By the mobility of chlorinated rubber known to three groups of data variations, surface viscosity and and its
The compatibility of his polymer such as phenol-formaldehyde resin modified is an important factor for influencing adhesive quality prepared therefrom.
The above specific embodiment only schematically illustrates the content of present invention, does not represent the limitation of the content of present invention.
It may occur to persons skilled in the art that be that specific embodiment can have other versions in the present invention.
Claims (9)
1. a kind of chlorinated rubber, according to the mass fraction, preparing raw material includes：100-130 parts of natural rubber, emulsifier 0.5-3
Part, 0.1-0.2 parts of dispersing agent, 0.1-3 parts of defoaming agent, 0.2-3 parts of nanometer additive, 0.1-1 parts of Sodium Allyl Sulfonate, initiator
0.1-1 parts, wherein nanometer additive and the mass ratio of Sodium Allyl Sulfonate are 1:1-1:5.
2. chlorinated rubber according to claim 1, which is characterized in that the raw material for preparing of the chlorinated rubber includes：Naturally
100-110 parts of rubber, 0.5-2 parts of emulsifier, 0.1-0.15 parts of dispersing agent, 0.1-2 parts of defoaming agent, 0.2-1 parts of nanometer additive,
0.1-0.6 parts of Sodium Allyl Sulfonate, 0.1-0.6 parts of initiator, wherein nanometer additive and the mass ratio of Sodium Allyl Sulfonate are
1:1-1:4。
3. chlorinated rubber according to claim 1 or 2, which is characterized in that the nanometer additive is nano tungsten disulfide.
4. chlorinated rubber according to claim 3, which is characterized in that the nano tungsten disulfide and Sodium Allyl Sulfonate
Mass ratio is 1:1-2.
5. a kind of preparation method of any chlorinated rubber of claim 1-4, includes the following steps：
(1) it by natural rubber after plasticating, dissolves by heating；
(2) Sodium Allyl Sulfonate, emulsifier, dispersing agent and defoaming agent is added, quickly stirs, adds initiator；
(3) it is passed through nitrogen discharge air into reaction system, above-mentioned reaction system is slowly heated up, is stirred simultaneously, slowly
It is passed through chlorine, the nanometer additive of half quality is added when temperature rises to 45-50 DEG C, 50 DEG C of maintenance is until chlorine intake reaches
To 40% or more；Continue to heat up, the nanometer additive of remaining half quality is added when temperature rises to 95-100 DEG C, at 150 DEG C
Being passed through for chlorine is completed before, and reaction was completed, leads to chlorine speed control in 35-45m3/h；
(4) regulator is added, is passed through oxygen and removes remaining chlorine, keep the temperature 1-1.5h；
(5) suspension is washed, depickling, filtering, drying, obtains chlorinated rubber powder.
6. preparation method according to claim 5, which is characterized in that the solvent in the step (1) is selected from：Chloroform, four
The mixed solution of one or both of chloromethanes；The mass fraction of solvent is 300-500 parts in the step (1)；The step
Suddenly leading to chlorine speed in (3) is 40m3/h；Regulator is n- dodecyl mereaptan in the step (4)；Depickling is handled in the step (5)
Selection is adjusted to neutrality with sodium bicarbonate；The drying mode is selected from：Spray drying, vacuum drying, freeze-drying, near-infrared are dry
One of with microwave drying.
7. any chlorinated rubber of claim 1-4 is preparing the purposes in ink, paint, coating or adhesive.
8. a kind of adhesive, the adhesive includes any chlorinated rubber of claim 1-4.
9. adhesive according to claim 8, which is characterized in that the adhesive further includes modified resin, thixotropic agent, fills out
Fill agent, preservative, plasticizer.
Priority Applications (1)
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| CN113527546A (en) * | 2021-08-17 | 2021-10-22 | 上海宝钱新材料技术有限公司 | Method for preparing chlorinated rubber by water phase method |
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| CN101481429A (en) * | 2009-01-13 | 2009-07-15 | 汪立波 | Industrial production method for producing chlorinated rubber by aqueous phase suspension |
| CN104817743A (en) * | 2015-04-15 | 2015-08-05 | 奉化市裕隆化工新材料有限公司 | Graphene modified chlorinated rubber composite material and preparation method thereof |
| CN105418809A (en) * | 2016-01-05 | 2016-03-23 | 临沂奥星化工有限公司 | Preparation method of chlorinated rubber |
| CN107840925A (en) * | 2017-12-13 | 2018-03-27 | 沈阳化工大学 | A kind of sulfonation gutta-percha preparation method |
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| CN101481429A (en) * | 2009-01-13 | 2009-07-15 | 汪立波 | Industrial production method for producing chlorinated rubber by aqueous phase suspension |
| CN104817743A (en) * | 2015-04-15 | 2015-08-05 | 奉化市裕隆化工新材料有限公司 | Graphene modified chlorinated rubber composite material and preparation method thereof |
| CN105418809A (en) * | 2016-01-05 | 2016-03-23 | 临沂奥星化工有限公司 | Preparation method of chlorinated rubber |
| CN107840925A (en) * | 2017-12-13 | 2018-03-27 | 沈阳化工大学 | A kind of sulfonation gutta-percha preparation method |
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| CN113527546A (en) * | 2021-08-17 | 2021-10-22 | 上海宝钱新材料技术有限公司 | Method for preparing chlorinated rubber by water phase method |
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Denomination of invention: A nano additive and sodium allyl sulfonate synergistically modified chlorinated rubber and its preparation method and application Effective date of registration: 20230728 Granted publication date: 20200929 Pledgee: Bank of Ningbo Co.,Ltd. Fenghua sub branch Pledgor: NINGBO HAOXIN YURON NEW MATERIAL CO.,LTD. Registration number: Y2023980050238 |