CN1597748A - Poly hydroxy multisulfide coupling agent and its preparation method and use - Google Patents
Poly hydroxy multisulfide coupling agent and its preparation method and use Download PDFInfo
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- CN1597748A CN1597748A CN 200410040364 CN200410040364A CN1597748A CN 1597748 A CN1597748 A CN 1597748A CN 200410040364 CN200410040364 CN 200410040364 CN 200410040364 A CN200410040364 A CN 200410040364A CN 1597748 A CN1597748 A CN 1597748A
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Abstract
A polyhydroxy-polysulfide coupling agent is prepared from pentaerythritol, halogen contained fatty acid, catalyst and water donor through proportional mixing, reaction, vacuum distilling to remove water donor, washing with hot water three times, cooling for crystallizing inw ater, dissolving and recrystallizing in absolute alcohol, adding sodium polysulfide, stirring, reacting, filtering to obtain deposit, water washing, and drying.
Description
One, technical field
The present invention relates to a kind of poly-hydroxy polysulfide coupling agents and its production and use, belonged to the preparation field of polymer processing aid.
Two, background technology
In polymer processing,, use coupling agent usually in order to improve good dispersiveness of consistency and the Chemical bond between mineral filler and the polymer.Rubber product (for example tire) is exactly a kind of typical high-performance, multifunctional composite goods.Be rubber item to be carried out reinforcement generally speaking by in rubber, sneaking into mineral filler.As everyone knows, although carbon black makes rubber product become black, it remains the effective reinforcing filler of rubber composite.White carbon black also is employed a kind of important reinforcing filler in the rubber industry.White carbon black can invest cross-linked rubber tear strength height, wear resistance is good and give birth to series of advantages such as heat is little.From saving the position of the energy, saving resource, people increase year by year for the requirement of the low fuel consumption of tire.Compare with carbon black, owing to have low-loss and the sliding property of moisture-proof, super emblem fine particle silica begins to become the hot topic of worldwide use in recent years as the reinforcing filler of tire tread glue.
Though yet the white carbon black particle shape is similar with carbon black, surface properties but differs widely.Its surface is covered by the silanol base, compares with carbon black, and practical situation are poor with the affinity of rubber, are difficult to obtain sufficiently high reinforcement.Aspect low-loss and wet and slippery property than more excellent.But aspect the strength at break and wear resistance relevant, at present also less than carbon black with reinforcement.Therefore, in order to obtain resembling high reinforcement the carbon black,, find to make rubber and white carbon black surface generation Chemical bond can improve reinforcement through research.As use silane coupling agent (for example, two～3～triethoxysilyl tetrasulfide, commodity are Si69) afterwards, can address this problem.Because this silane coupling agent is a liquid, facile hydrolysis can produce ethanol, Si69 and SiO in mixing process
2The silicon hydroxyl need under comparatively high temps, to act on, and under this this temperature the easy incipient scorch of alcoholysis, difficulty often takes place aspect processing.Because this coupling agent costs an arm and a leg, its admixtion is very big again, has improved the cost of sizing material in addition.Therefore, at rubber circle, silane coupling agent is wanted large-area application, and very big difficulty is still arranged.In order to seek silane coupling material in addition, people once did a lot of effort in recent years.
Te Kaiping has proposed for 7～No. 330959 the anionoid polymerization end is carried out coupling with tertiary amine compounds such as diglycidylaniline, and the result can satisfy the silica compound of sliding property, rolling resistance and wear resistant catalyzer face rubber of tire moisture-proof simultaneously.It is that the anion active rubber terminal is adopted the end capped terminal alkyl TMOS modified rubber of halo-alkoxides silane compound that the spy opens clear 62～No. 227908 patents.Te Kaiping has narrated employing epoxidation conjugated diolefine hydrocarbon system rubber for 9～No. 241429 and white weighting agent reacts.Thereby, even also can make epoxidezed rubber and white carbon black form Chemical bond, improve outer epistasis without silane coupling agent, because the dispersiveness of white carbon black also improves, can obtain the better physical performance simultaneously.All increase at aspects such as intensity, heat generation and wear resistancies.
Above several method all is earlier rubber to be carried out modification, makes the certain polar group of generations on its high-polymer molecular chain, thus promote to a certain extent rubber with the coupling between the carbon black in vain, combine.But these methods all must increase an independent modified rubber operation, and actually operating is got up also cumbersome.
Three, summary of the invention
The objective of the invention is provides a kind of poly-hydroxy polysulfide coupling agents and its production and use at the deficiency that has modification technology now.Be characterized in that this coupling agent is a pressed powder, the mineral filler water content is not had particular requirement, can not cause scorching with the effect of silicon hydroxyl at low temperatures, can replace silane coupling agent fully.
The objective of the invention is to realize that by following technical measures wherein said raw material material umber is parts by weight except that specified otherwise.
The formula constituent of poly-hydroxy polysulfide coupling agents is:
75～150 parts of tetramethylolmethanes
52～118 parts in Halogen lipid acid
30～100 parts of polysulfides
1～15 part of catalyzer
200～800 parts in band aqua
Wherein Halogen lipid acid is Mono Chloro Acetic Acid or chloropropionic acid; Polysulfide is any in sodium disulfide, the sodium tetrasulfide; The band aqua is any in the benzene,toluene,xylene; Catalyzer be in sulfuric acid, sodium pyrosulfate, hydrochloric acid, the iron(ic) chloride any.
The preparation method of poly-hydroxy polysulfide coupling agents
With 75～150 parts of tetramethylolmethanes, 52～118 parts in Halogen lipid acid, 1～15 part of catalyzer, 200～800 parts of addings of band aqua have agitator, thermometer, in the reactor of water trap and reflux exchanger, in 80～160 ℃ of 0.5～8 hour reaction times of temperature, treat that water layer in the water trap no longer increases till, be warming up to 80～160 ℃, steam the band aqua, with hot wash three times, reduce by 5～10 ℃ of crystallizations in water of temperature, use the anhydrous alcohol solution recrystallization, obtain white monoesters crystal, again with the monoesters crystal molten with dehydrated alcohol in, add 30～100 parts of sodium polysulphide, continue to stir, in 30～50 ℃ of reactions of temperature 0.1～8 hour, throw out is through filtering washing, drying, obtain poly-hydroxy and vulcanize coupling agent more, its structure is:
X=2 or 4 wherein.
This coupling agent is yellowish pressed powder, and no fusing point is slightly soluble in ethanol, and methyl alcohol is dissolved in hot dimethyl formamide (DMF); 113 ℃ begin to be decomposed into free radical.
This coupling agent is mainly used in mineral filler and natural rubber, styrene-butadiene rubber(SBR), isoprene-isobutylene rubber, the coupling agent of chloroprene rubber or cis-1,4-polybutadiene rubber.
The present invention has the following advantages:
1, nontoxic, synthetic method is simple, and is easy to use;
2, be pressed powder, the mineral filler water content is not had particular requirement, can not cause the scorching phenomenon with the effect of silicon hydroxyl at a lower temperature;
3, well improve consistency between rubber and the filler, processing characteristics reduces the interaction between weighting agent-weighting agent;
4, this coupling agent has good coupled action between mineral filler and rubber, reduces to add the by product that produce man-hour;
5, can replace silane coupling agent fully.
Four, embodiment
Below by embodiment the present invention is specifically described; it is important to point out that present embodiment only is used for the present invention is further specified; can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can make some nonessential improvement and adjustment according to the content of foregoing invention.
Embodiment
1. tetramethylolmethane 75 is restrained, Mono Chloro Acetic Acid 52 grams, benzene 200 grams, sodium pyrosulfate 3 grams add and have agitator, and thermometer is in the reactor of water trap and reflux exchanger, till temperature was reacted 4 hours for 90 ℃, treated that water layer no longer increases in the water trap.Be warming up to 90 ℃ of decompressions and steam the band aqua, with hot wash three times,, use the anhydrous alcohol solution recrystallization in 5 ℃ of crystallizations in water of temperature, obtain white monoesters crystal 87 grams, then the monoesters crystal is dissolved in 300 milliliters of dehydrated alcohols, adds sodium tetrasulfide 35 grams again, continue to stir 4 hours, throw out after filtration, washing, drying obtains the poly-hydroxy polysulfide coupling agents.
2. tetramethylolmethane 112 is restrained, Mono Chloro Acetic Acid 78 grams, toluene 300 grams, the vitriol oil 15 grams add and have agitator, and thermometer is in the reactor of water trap and reflux exchanger, till temperature was reacted 4 hours for 120 ℃, treated that water layer no longer increases in the water trap.Be warming up to 120 ℃ of decompressions and steam band aqua toluene, with hot wash three times, in 8 ℃ of crystallizations in water of temperature, use the anhydrous alcohol solution recrystallization, obtain white monoesters crystal 97 grams, then the monoesters crystal is dissolved in 400 milliliters of dehydrated alcohols, add sodium tetrasulfide 37 grams again, continue to stir, in 40 ℃ of reactions of temperature 4 hours, throw out was washed after filtration, drying obtains the poly-hydroxy polysulfide coupling agents.
3. tetramethylolmethane 150 is restrained, chloropropionic acid 118 grams, dimethylbenzene 600 grams, iron(ic) chloride 12 grams add and have agitator, and thermometer is in the reactor of water trap and reflux exchanger, till temperature was reacted 6 hours for 150 ℃, treated that water layer no longer increases in the water trap.Be warming up to 140 ℃ of decompressions and steam band aqua dimethylbenzene, with hot wash three times, in 10 ℃ of crystallizations in water of temperature, use the anhydrous alcohol solution recrystallization, obtain white monoesters crystal 130 grams, then the monoesters crystal is dissolved in 400 milliliters of dehydrated alcohols, add sodium disulfide 47 grams again, continue to stir, in 50 ℃ of reactions of temperature 4 hours, throw out was washed after filtration, drying obtains the poly-hydroxy polysulfide coupling agents.
Application example
1, the test recipe of matrix material
70 kilograms of natural rubbers; 10 kilograms of cis-butadiene cements; 20 kilograms of butadiene-styrene rubbers; 2.5 kilograms of Sulfurs; 0.25 kilogram of dithio tetra methylthiuram (TMTD); 1.8 kilograms of N cyclohexyl 2 benzothiazole sulfenamides (CZ); 30 kilograms of carbon black CBN330; 50 kilograms of carbon black CBN751; 1 kilogram in lipid acid; 5 kilograms in zinc oxide; 8 kilograms of Stockholm tars; 1 kilogram in paraffin; 30 kilograms of deposition white carbon blacks; The coupling agent consumption is 1～5% of a white carbon black weight.
2, rubber mixing technique bar
The 35L Banbury mixer, 80 ℃ of roller temperature
3, cure conditions
150 ℃ * 8 minutes
4, physical and mechanical properties test sees for details shown in table 1 and the table 2.
Learn that from table 1 adding of properties-correcting agent has improved the dispersiveness of inorganic powder silicon-dioxide, improved the physicals of rubber, improved the tensile strength and the tensile modulus of cross-linked rubber.Hardness slightly reduces, and tensile strength can improve 20%, and stretching surely has obvious enhancing.
Learn that from table 2 disulphide improves a lot than " T10 " of tetrasulfide, that is, thermostability strengthens, and the incipient scorch phenomenon weakens.
Table 1
| Number blank #1 #2 test method |
| Conditions of vulcanization (making by oneself) hardness (A) degree 80 74 75 GB531 hot strengths (M) are not less than 11.5 13.6 12.3 GB528,200% stretching strength (M) and are not less than/and 6.69 8.2 GB528 elongations at break (%) are not less than 179 336 269 GB528 T10 (second) 120 25 35 |
| Remarks: (1) " blank " is that 20 parts of unmodified WBC (2) #1 is that properties-correcting agent (3) #2 of 20 parts of WBC and 1% is 20 parts of WBC and 2% properties-correcting agent, and (4) properties-correcting agent is the pentaerythritol ester tetrasulfide |
Table 2
| Number 150 ℃ of blank #1 #2 test method cure conditions (making by oneself) * 8 150 ℃ * 8 |
| Hardness (A) degree 74 72 72 GB531 hot strengths (M) are not less than 21.5 20.6 20.8 GB528,200% stretching strength (M) and are not less than 11.1 7.1 7.2 GB528 elongations at break (%) and are not less than 404 470 490 GB528 compression sets (120 * 24H, % are not more than 688 T10 (second) 60 53 53 |
| Conclusion: (1) " blank " is 33 parts of WCB and part SI69 modification thereof, T10:1 minute; (2) 33 parts of WCB of #1 seriation and 1 part of properties-correcting agent, T10:53 second; (3) #2 is 33 parts of WCB and 1 part of properties-correcting agent, parks 24H.(4) properties-correcting agent is pentaerythritol ester disulphide |
Annotate: in above each table, WCB represents white carbon black, and " T10 " expression rubber admixtion vulcanizes in sulfidation finishes 10%.
Claims (5)
1. poly-hydroxy polysulfide coupling agents is characterized in that the recipe ingredient of this coupling agent is by weight:
75～150 parts of tetramethylolmethanes
52～118 parts in Halogen lipid acid
30～100 parts of polysulfides
1～15 part of catalyzer
200～800 parts in band aqua
Wherein Halogen lipid acid is Mono Chloro Acetic Acid or chloropropionic acid, and polysulfide is any in sodium tetrasulfide or the sodium disulfide.
2. according to the described poly-hydroxy polysulfide coupling agents of claim 1, it is characterized in that catalyzer is a sulfuric acid, sodium pyrosulfate, any in hydrochloric acid or the iron(ic) chloride.
3. according to the described poly-hydroxy polysulfide coupling agents of claim 1, it is characterized in that being with aqua is benzene, any in toluene or the dimethylbenzene.
4. according to the preparation method of the described poly-hydroxy polysulfide coupling agents of claim 1～3, it is characterized in that:
With tetramethylolmethane 75～150 weight parts, 52～118 parts of weight parts of Halogen lipid acid, catalyzer 1～15 weight part and band aqua 200～800 weight parts add and have agitator, thermometer is in the reactor of water trap and reflux condensing tube, in 80～160 ℃ of reactions of temperature 0.5～8 hour, till treating that water layer in the water trap no longer increases, be warming up to 80～160 ℃ of decompressions and steam the band aqua,, be cooled to 5～10 ℃ with hot wash three times, crystallization in water, use the anhydrous alcohol solution recrystallization then, obtain white monoesters crystal, again the monoesters crystal is dissolved in the dehydrated alcohol, add sodium polysulphide 30～100 weight parts, continue to stir, in 30～50 ℃ of reactions of temperature 0.1～8 hour, throw out after filtration, washing, drying obtains the poly-hydroxy polysulfide coupling agents, and its structure is:
X=2 or 4 wherein.
5. according to the purposes of the described poly-hydroxy polysulfide coupling agents of claim 1～4, its feature is mainly used in mineral filler and natural rubber at this coupling agent, styrene-butadiene rubber(SBR), isoprene-isobutylene rubber, the coupling agent of chloroprene rubber or cis-1,4-polybutadiene rubber.
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| CN1228370C CN1228370C (en) | 2005-11-23 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102822145A (en) * | 2010-04-12 | 2012-12-12 | 切弗朗菲利浦化学公司 | Oligomerization of bis(beta-hydroxy) polysulfides through etherification |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102822145A (en) * | 2010-04-12 | 2012-12-12 | 切弗朗菲利浦化学公司 | Oligomerization of bis(beta-hydroxy) polysulfides through etherification |
| CN102822145B (en) * | 2010-04-12 | 2014-12-24 | 切弗朗菲利浦化学公司 | Oligomerization of bis(beta-hydroxy) polysulfides through etherification |
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| CN1228370C (en) | 2005-11-23 |
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