CN103249744B - Solid natural rubber and method for producing same - Google Patents
Solid natural rubber and method for producing same Download PDFInfo
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- CN103249744B CN103249744B CN201180058857.3A CN201180058857A CN103249744B CN 103249744 B CN103249744 B CN 103249744B CN 201180058857 A CN201180058857 A CN 201180058857A CN 103249744 B CN103249744 B CN 103249744B
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- natural rubber
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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
- C08C1/00—Treatment of rubber latex
- C08C1/02—Chemical or physical treatment of rubber latex before or during concentration
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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
- C08C19/08—Depolymerisation
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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Abstract
This method for producing a solid natural rubber involves: a radical-generating-agent addition step of adding a radical-generating agent to a natural rubber latex and advancing an oxidation reaction of cutting the molecular chains of the rubber; and a solidification step of drying and solidifying the natural rubber latex after the oxidation reaction and thereby obtaining a natural rubber that does not contain any aldehyde groups in the molecular chains thereof. The obtained solid natural rubber is reduced in molecular weight because the molecular chains have been cut, and does not contain any aldehyde groups in the molecular chains. Thus, the solid natural rubber is provided with a desired viscosity even without being masticated, and the viscosity thereof is less likely to increase during storage.
Description
Technical field
The present invention relates to does not need to plasticate and viscosity is not easy solid natural rubber along with the time changes and manufacture method thereof.
Background technology
Natural rubber has the character that tensile strength is large, vibrate the excellences such as the heating caused is few.Therefore, all the time, as the various rubber item such as tire, vibration-proof rubber, band, rubber gloves raw material and use.The solid natural rubber circulated as the manufacture raw material of rubber item is divided into visual rating scale rubber (VGR) and technically classified rubber (TSR) substantially.In VGR, representational is rubber smoked sheet (RSS) based on " the international quality packing specificationss (being commonly called as Green Book) of natural rubber various grade product " classification.Such as, RSS is following manufacture.First, add after the acid such as formic acid, acetic acid makes it to solidify in fresh latex, be placed on operator's console, stretch with rod and adjust thickness.Then, divide with the limit stretching, extension limit water squeezing of waveform (rib-like) roller thus be configured as sheet.Then, the sheet of shaping being hung a couple of days makes it dry.Then, wash with water dried without rubber smoked sheet (USS), sootiness a couple of days makes it dry.In addition, TSR manufactures like this: the micronize by raw material pulverizing such as glue cup blocks (cup lump) (material of fresh latex natural coagulation in collection cups), after washing with water, by its warm air drying.
The solid natural rubber molecular weight of such manufacture is large, viscosity is high.Therefore, when using the manufacture raw material of the solid natural rubber such as RSS as rubber item, in order to reduce viscosity to improve processibility, need to plasticate in advance.
Existing patent documentation
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2003-320524 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2003-313366 publication
Patent documentation 3: Japanese Unexamined Patent Publication 2009-275165 publication
Patent documentation 4: Japanese Unexamined Patent Publication 9-136903 publication
Summary of the invention
the problem that invention will solve
When plasticating, the molecular chain of rubber is cut off, and molecular weight reduces.Thus, the viscosity of the solid natural rubbers such as RSS can be reduced.But, RSS etc. is directly plasticated (dry type refining) time, be difficult to its entirety to be refined equably.Therefore, produce the deviation of viscosity in same batch because position is different, or batch between easily produce the deviation of viscosity.In addition, originally just there is the deviation of viscosity in RSS etc.Therefore, even in the rubber after plasticating, viscosity also easily produces deviation.In addition, light carries out plasticating and just process number is increased.Therefore, the manufacturing time of rubber item is elongated, and cost uprises.
In addition, plasticate in operation, to solid natural rubber heating, thus by molecular chain scission.Now, when the end of cut-off molecular chain is oxidized, generate aldehyde radical, hydroxyl etc.Aldehyde radical is the bonding again because of aldol condensation easily.Namely known, when aldehyde radical generates, due to cut-off molecular chain likely bonding again of plasticating.The rubber after plasticating is made to increase in storage period viscosity thus.
Such as, in above-mentioned patent documentation 4, as the manufacture method of liquid depolymerized natural rubber, disclose to have and add carbonyl compound in natural rubber latex Ruzhong, the method for oxidation by air under the existence of free-radical generating agent.Wherein, carbonyl compound and the molecular end bonding of the natural rubber be depolymerizated, play the effect (paragraph [0013] of patent documentation 4) suppressing repolymerization.That is, according to the method disclosed in patent documentation 4, in order to suppress the cut-off molecular chain bonding again caused by the aldehyde radical generated, carbonyl compound is added.
The present invention completes based on such situation, even if problem be to provide do not carry out plasticating also there is desired viscosity and store time viscosity be also not easy rise solid natural rubber and manufacture method.
for the scheme of dealing with problems
(1) in order to solve above-mentioned problem, the feature of solid natural rubber of the present invention is, it is quantized by low molecule by the cut-out of molecular chain, not containing aldehyde radical in this molecular chain.
Existing solid natural rubber, by plasticating the molecular chain scission of rubber, is quantized by low molecule thus, and is adjusted to desired viscosity.But as mentioned above, when plasticating, the end of molecular chain generates aldehyde radical etc.
On the other hand, although solid natural rubber of the present invention is also quantized by low molecule by the cut-out of molecular chain, and be adjusted to desired viscosity, not containing aldehyde radical in molecular chain.Therefore, the possibility that the viscosity that storage period is caused by the bonding again of aldehyde radical rises is little.In addition, owing to being adjusted to desired viscosity, so need not plasticate.Therefore, solid natural rubber of the present invention can directly as rubber item manufacture raw material and use.Therefore, when adopting solid natural rubber of the present invention, solve the problem of the viscosity deviation produced in the rubber after in the past plasticating.In addition, due to operation of plasticating can be omitted, thus process number can be cut down.Its result, can realize the shortening of the manufacturing time of rubber item and the reduction of cost.It should be noted that, in the present invention, " not containing aldehyde radical " means: use Varian MedicalSystems, the NMR(nucleus magnetic resonance that Inc. manufactures) device " INOVA-400 "
1h-NMR does not detect the displacement being derived from aldehyde radical in measuring.
(2) in addition, the feature of the manufacture method of solid natural rubber of the present invention is, it has: the operation of adding free-radical generating agent, adds free-radical generating agent, make the oxidizing reaction of the molecular chain scission of rubber carry out in natural rubber latex Ruzhong; And curing process, make it solidify the natural rubber latex drying after this oxidizing reaction, obtain the natural rubber not containing aldehyde radical in this molecular chain thus.
the effect of invention
Utilize manufacture method of the present invention, by under latex state by the molecular chain scission of rubber, the viscosity of the natural rubber after solidification can be adjusted.In manufacture method of the present invention, the cut-out of molecular chain and oxidizing reaction were at room temperature carried out about several minutes ~ a few hours, can be shown specifically in embodiment described later.Therefore, need not arrange especially heating installation just can easily and stably carry out solid natural rubber viscosity adjustment.In addition, compared with the situation of plasticate (dry type is refined), latex entirety can be made to react equably by the cut-out and oxidizing reaction carrying out molecular chain in the liquid state.Batch therefore, be not easy between to produce viscosity deviation.
In addition, the solid natural rubber obtained is adjusted to desired viscosity.Therefore, can carry out plasticating and the direct manufacture raw material being used as rubber item.That is, when utilizing manufacture method of the present invention, can manufacture by natural rubber latex the solid natural rubber not needing to plasticate.Due to can operation of plasticating be omitted, therefore, it is possible to cut down process number.Its result, can realize the shortening of the manufacturing time of rubber item and the reduction of cost.In addition, not containing aldehyde radical in the molecular chain of the solid natural rubber obtained.Therefore, the viscosity of the solid natural rubber in storage can be suppressed to rise.
Accompanying drawing explanation
Fig. 1 is the figure of the Mooney viscosity value representing the solid natural rubber corresponding with the addition of free-radical generating agent.
Embodiment
Below, the embodiment of solid natural rubber of the present invention and manufacture method thereof is described.It should be noted that, solid natural rubber of the present invention and manufacture method thereof are not limited to following embodiment, and in the scope not departing from purport of the present invention, those skilled in the art can implement to have implemented the various forms such as change, improvement.
< solid natural rubber >
Solid natural rubber of the present invention is quantized by low molecule by the cut-out of molecular chain, not containing aldehyde radical in this molecular chain.Quantize about low molecule, be only less than the molecular weight of the solid natural rubber of not plasticating in the past such as RSS.Quantized by low molecule, the viscosity degradation of solid natural rubber.Such as, the weight-average molecular weight of gel permeation chromatography (GPC) is utilized to be 1 × 10
6below.In addition, from viewpoints such as processibilities, the mooney viscosity [ML (1+3) 121 DEG C] of solid natural rubber can be less than 80.Mooney viscosity [ML (1+3) 121 DEG C] is more than 30 and less than 70 is more suitably.In this specification sheets, mooney viscosity adopts according to JIS K6300-1(2001) value that measures.In addition, as mentioned above, the presence or absence of aldehyde radical is passed through to use Varian Medical Systems, the NMR device " INOVA-400 " that Inc. manufactures
1h-NMR measures and judges.
Solid natural rubber of the present invention can be added with the natural rubber latex solidification of free-radical generating agent and obtain.Below, the manufacture method of solid natural rubber of the present invention is described.
The manufacture method > of < solid natural rubber
The manufacture method of solid natural rubber of the present invention has the operation and curing process of adding free-radical generating agent.Below, each operation is described.
(1) operation of free-radical generating agent is added
This operation is following operation: add free-radical generating agent in natural rubber latex Ruzhong, make the oxidizing reaction of the molecular chain scission of rubber carry out.As natural rubber latex, use and adopt the fresh latex of liquid by rubber tapping (Tapping), add the latex (high ammonia latex) of ammonia treatment wherein.For the rubber constituent (dry rubber quality, identical below) of natural rubber latex, there is no particular limitation for concentration.When rubber constituent concentration is too low, the solid natural rubber obtained tails off, uneconomical.On the contrary, during rubber constituent excessive concentration, the rubber constituent in latex becomes unstable, causes the gathering between rubber grain, be difficult to carry out oxidizing reaction equably in oxidizing reaction.Such as, preferably rubber constituent concentration is set to more than 10 quality % and below 60 quality %.
As free-radical generating agent, use be selected from peroxidation system free-radical generating agent, reducto oxydative system free-radical generating agent, azo system free-radical generating agent more than one.As peroxidation system free-radical generating agent, Potassium Persulphate (KPS), ammonium persulphate (APS), benzoyl peroxide (BPO), hydrogen peroxide, cumene hydroperoxide, tertbutyl peroxide (TBHPO), ditertiary butyl peroxide, 2,2-Diisopropyl azodicarboxylates etc. can be listed.As reducto oxydative system free-radical generating agent, be used for, with the reductive agent of peroxide combination, tetren (TEPA), thio-alcohol, sodium acid sulfite, reducing metal ion, xitix etc. can being listed.As preferably combining example, TBHPO and TEPA, hydrogen peroxide and Fe can be listed
2+salt, KPS and sodium acid sulfite etc.As azo system free-radical generating agent, Diisopropyl azodicarboxylate, azo two methyl isobutyrate, azo two cyclohexanenitrile, azobisisobutylonitrile base amidine hydrochloride, 4,4'-azos two (4-cyanopentanoic acid) etc. can be listed.Wherein, from adopting on a small quantity, large, that temperature of reaction can be made the to produce impact of effect stablizes the reason of carrying out viscosity adjustment littlely, preferably uses at least one in Potassium Persulphate (KPS), ammonium persulphate (APS), benzoyl peroxide (BPO).
In order to the solid natural rubber obtained is adjusted to desired viscosity, the addition of free-radical generating agent can determine according to the kind of free-radical generating agent is suitable.By increasing and decreasing the addition of free-radical generating agent, the viscosity of solid natural rubber can be adjusted.Such as, when the addition of free-radical generating agent is very few, the cut-out of molecular chain and oxidizing reaction are difficult to carry out, and therefore become and are difficult to be adjusted to low viscosity.On the contrary, the interpolation of superfluous free-radical generating agent is also uneconomical.Such as, relative to the 100 mass parts rubber constituents in natural rubber latex Ruzhong, it is desirable to the addition of free-radical generating agent to be set to more than 0.1 mass parts and below 5 mass parts.
The cut-out of molecular chain and oxidizing reaction can at room temperature stir the natural rubber latex limit being added with free-radical generating agent and carry out in limit.In addition, the reaction times can viscosity as required and adjusting, or be set to several minutes ~ and about a few hours.
(2) curing process
This operation is following operation: make it solidify the natural rubber latex drying after this oxidizing reaction, obtains the natural rubber not containing aldehyde radical in molecular chain thus.For the drying means of natural rubber latex, there is no particular limitation.Spraying dry, revolver drier, conveyor dryer etc. is utilized to carry out.Consider the deterioration of the rubber caused by thermal conductance, remove moisture well from the view point of efficiency, drying temperature is preferably set to about 50 ~ 200 DEG C.In addition, drying treatment preferably terminated within several minutes.It should be noted that, about the suitable mooney viscosity of the solid natural rubber obtained and the determination methods with or without aldehyde radical, as mentioned above.
Embodiment
Then, the present invention is further illustrated by enumerating embodiment.
The manufacture > of < solid natural rubber
[embodiment 1]
As natural rubber latex, use the high ammonia latex (rubber constituent concentration 60.2 quality %, ammonia constituent concentration 0.7 quality %) that Goldenhope company (Malaysian state) makes.First, high ammonia latex being diluted to rubber constituent concentration is 30 quality %.Then, relative to the rubber constituent 100g of the latex of dilution, add the free-radical generating agent Potassium Persulphate (KPS) of specified amount, at room temperature stir 10 minutes.Then, reacted latex is dry in the baking oven of 50 DEG C, thus solidification.So obtain the solid natural rubber of embodiment 1.
[embodiment 2]
Free-radical generating agent is changed to ammonium persulphate (APS), in addition, operate similarly to Example 1, obtain the solid natural rubber of embodiment 2.
[embodiment 3]
Free-radical generating agent is changed to benzoyl peroxide (BPO), in addition, operate similarly to Example 1, obtain the solid natural rubber of embodiment 3.
< viscosimetric analysis >
For the solid natural rubber obtained, measure mooney viscosity.The mensuration of mooney viscosity uses TOYO SEIKI SEISAKU-SHO, the rotor-type mooney's viscosimeter that LTD. manufactures.Then, the rotating speed of L shape rotor is set to 2rpm, measures temperature and be set to 121 DEG C, after carrying out preheating in 1 minute, measure the mooney viscosity after 3 minutes.The Mooney viscosity value of the solid natural rubber that Fig. 1 display is corresponding with the addition of free-radical generating agent.
As shown in Figure 1, by adding free-radical generating agent to natural rubber latex Ruzhong, the mooney viscosity of solid natural rubber reduces.In addition, as embodiment 1(KPS), shown in the curve of embodiment 2 (APS), the mooney viscosity of solid natural rubber increases along with the addition of free-radical generating agent and reduces.According to confirming above, utilize manufacture method of the present invention can manufacture the solid natural rubber with desired viscosity.
utilizability in industry
Utilize the present invention easily can obtain having the solid natural rubber of desired viscosity.And can operation of plasticating be omitted.Thus, the problem of the viscosity deviation produced in the rubber after plasticating is solved.In addition, the shortening of manufacturing time and the reduction of cost of rubber item can be realized.In addition, based on solid natural rubber of the present invention, viscosity during storage rises also few.Therefore, solid natural rubber of the present invention is useful as the manufacture raw material of rubber item.
Claims (4)
1. a solid natural rubber, it is characterized in that, the natural rubber latex solidification being only added with more than one the free-radical generating agent be selected from Potassium Persulphate, ammonium persulphate, benzoyl peroxide obtains by it, this solid natural rubber is quantized by low molecule by the cut-out of molecular chain, not containing aldehyde radical in this molecular chain, wherein, relative to the 100 mass parts rubber constituents in described natural rubber latex Ruzhong, the addition of described free-radical generating agent is more than 0.1 mass parts and below 5 mass parts.
2. solid natural rubber according to claim 1, wherein, mooney viscosity [ML (1+3) 121 DEG C] is less than 80.
3. a manufacture method for solid natural rubber, is characterized in that, it has:
Add the operation of free-radical generating agent, more than one the free-radical generating agent be selected from Potassium Persulphate, ammonium persulphate, benzoyl peroxide is only added in natural rubber latex Ruzhong, at room temperature stir, make the oxidizing reaction of the molecular chain scission of rubber carry out thus; And
Curing process, makes it solidify the natural rubber latex drying after this oxidizing reaction, obtains the natural rubber not containing aldehyde radical in this molecular chain thus,
Wherein, relative to the 100 mass parts rubber constituents in described natural rubber latex Ruzhong, the addition of described free-radical generating agent is more than 0.1 mass parts and below 5 mass parts.
4. the manufacture method of solid natural rubber according to claim 3, wherein, the mooney viscosity [ML (1+3) 121 DEG C] of the described natural rubber obtained in described curing process is less than 80.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010271681A JP5745831B2 (en) | 2010-12-06 | 2010-12-06 | Solid natural rubber and method for producing the same |
| JP2010-271681 | 2010-12-06 | ||
| PCT/JP2011/078061 WO2012077633A1 (en) | 2010-12-06 | 2011-12-05 | Solid natural rubber and method for producing same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103249744A CN103249744A (en) | 2013-08-14 |
| CN103249744B true CN103249744B (en) | 2015-06-10 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201180058857.3A Active CN103249744B (en) | 2010-12-06 | 2011-12-05 | Solid natural rubber and method for producing same |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP5745831B2 (en) |
| CN (1) | CN103249744B (en) |
| MY (1) | MY163195A (en) |
| WO (1) | WO2012077633A1 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6087176B2 (en) * | 2013-03-07 | 2017-03-01 | 東洋ゴム工業株式会社 | Modified polymer production method and diene polymer |
| DE112014001128T5 (en) | 2013-03-07 | 2015-12-10 | Toyo Tire & Rubber Co., Ltd. | Process for the preparation of a modified polymer and rubber composition |
| JP5900526B2 (en) * | 2014-03-27 | 2016-04-06 | 横浜ゴム株式会社 | Rubber composition and pneumatic tire using the same |
| WO2019102109A1 (en) * | 2017-11-23 | 2019-05-31 | Compagnie Generale Des Etablissements Michelin | Natural rubber |
| CN108424530B (en) * | 2018-03-14 | 2021-05-07 | 中国化工株洲橡胶研究设计院有限公司 | Preparation method of eucommia ulmoides latex |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1310196A (en) * | 2000-01-24 | 2001-08-29 | 日东电工株式会社 | Process for producing natural rubber for pressure-sensitive adhesive and pressure-sensitive adhesive composition based on natural rubber |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3606745A1 (en) * | 1986-03-01 | 1987-09-03 | Huels Chemische Werke Ag | METHOD FOR MOLECULAR WEIGHT REDUCTION OF NATURAL RUBBER IN LATEX FORM |
| JP3517500B2 (en) * | 1995-11-10 | 2004-04-12 | 花王株式会社 | Method for producing depolymerized natural rubber |
| JP2001261707A (en) * | 2000-03-23 | 2001-09-26 | Okayama Prefecture | Method of depolymerizing natural rubber |
| JP5086557B2 (en) * | 2006-04-03 | 2012-11-28 | 株式会社ブリヂストン | Rubber composition and pneumatic tire using the same |
| JP2007277450A (en) * | 2006-04-10 | 2007-10-25 | Mitsubishi Gas Chem Co Inc | Low-molecular weight natural rubber |
| JP2009013278A (en) * | 2007-07-04 | 2009-01-22 | Sumitomo Rubber Ind Ltd | Method for producing depolymerized natural rubber |
-
2010
- 2010-12-06 JP JP2010271681A patent/JP5745831B2/en active Active
-
2011
- 2011-12-05 MY MYPI2013700920A patent/MY163195A/en unknown
- 2011-12-05 WO PCT/JP2011/078061 patent/WO2012077633A1/en active Application Filing
- 2011-12-05 CN CN201180058857.3A patent/CN103249744B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1310196A (en) * | 2000-01-24 | 2001-08-29 | 日东电工株式会社 | Process for producing natural rubber for pressure-sensitive adhesive and pressure-sensitive adhesive composition based on natural rubber |
Also Published As
| Publication number | Publication date |
|---|---|
| MY163195A (en) | 2017-08-15 |
| JP5745831B2 (en) | 2015-07-08 |
| CN103249744A (en) | 2013-08-14 |
| WO2012077633A1 (en) | 2012-06-14 |
| JP2012121946A (en) | 2012-06-28 |
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