CN101665585A - Method for preparing ternary complex antiager and emulsion and application thereof in neoprene - Google Patents
Method for preparing ternary complex antiager and emulsion and application thereof in neoprene Download PDFInfo
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Abstract
The invention provides a method for preparing ternary complex antiager and an emulsion and an application thereof in neoprene. The ternary complex antiager is prepared by formulation and mixing of a bisphenol mono-acrylate antiager, a hindered phenolic antiager and a sulfoether antiager according to specified proportioning. The preparation method comprises the following steps: dissolving the ternary complex antiager prepared by the above method with an organic solvent at room temperature; adding an emulsifying agent prepared by the mixture of disproportionated rosin acid soap water solution and sulfoacid anionicsurfactant water solution for fully mixing; and obtaining the ternary complex antiager emulsion after dispersing. In the process of synthesizing the neoprene rubber latex, the ratioof the dry glue of the neoprene in terms of the added ternary complex antiager emulsion is 1:0.03-0.07. The research of an aging test shows that the neoprene product prepared by adding the ternary complex antiager emulsion of the invention is superior to the neoprene product prepared by using the antiager BHT in the aspects of appearance color, Mooney viscosity, Mooney scorch time and mechanicalintensity property indexes.
Description
Technical field
The manufacture method that the present invention relates to a kind of ternary composite type anti-aging agent, emulsion reaches in producing chloroprene rubber to be used, to obtain having the chloroprene rubber product of stability.The ternary composite type anti-aging agent is a raw material by a kind of bisphenolmonoacryates oxidation inhibitor and a kind of Hinered phenols antioxidant and a kind of thioether oxidation inhibitor, makes after composite.
Background technology
Chloroprene rubber is to be main raw material with the chlorbutadiene, a kind of elastomerics that obtains by homopolymerization or copolymerization.Prove by its crystallization behavior and infrared absorption spectrum analysis, mainly contain the unitary linear chain link of trans 2-chloro-2-butylene in the main chain of chloroprene rubber, as:
The mechanical property of chloroprene rubber is decided by polymeric microtexture, and processing characteristics depends on polymeric molar mass and distribution thereof, and side chain and crosslinked number and distribution.
The goods of chloroprene rubber have satisfactory stability and ageing resistance, but the package stability of its rubber is relatively poor, with the shelf-time growth, catabiosis occurs.Its basic reason is to exist active pair of key on the molecular chain of rubber, be easy to be subjected to the attack of oxygen and oxidizing reaction takes place, especially under the effect that is subjected to factors such as light, heat, oxygen, catalyst residue, produce the active centre in the middle of being easy to make molecular chain, the reaction of propagation of chain and branching, crosslinking reaction, both ageing of rubber take place then.The performance degradation of the easy hardening of rubber, plasticity reduction, time of scorch shortening, appearance color flavescence, Mooney viscosity increase, processing characteristics and cross-linked rubber after aging.
In order to prepare a kind of chloroprene rubber with stability, need to add effective anti-aging agent in the production process, to prevent rubber in drying, storage, the course of processing, original chemical constitution and molecular structure change.The fundamental property that keeps the product regulation.In the ageing research process, neoprene rubber Mooney viscosity, time of scorch, appearance color, the velocity of variation of these indexs will characterize out chloroprene rubber product aging destructiveness.
Technology in the past adopts antioxidant BHT (chemical name: 2,6 di tert butyl 4 methyl phenol) be anti-aging agent usually.Polymer Degradation and Stability, 1993,39 (3): researchs such as 317-328.Shin ' ichi are thought, the contraposition of BHT hydroxyl is a methyl, as chain termination type oxidation inhibitor, provide hydrogen atom after, the benzene oxyradical of formation is easy to take place the bimolecular condensation reaction, generate 1,2-ethylene dialkyl group phenol EPB or methyne quinones dipolymer SBQ.As shown in the figure.
Bimolecular condenses EPB or SBQ can directly cause the outward appearance flavescence of chloroprene rubber product.
Specialty elastomer goods .2004.25 (5) 23～24 discloses the method that the anti-BHT of a kind of phosphite ester kind antioxidant TNPP and phenolic antioxidant makes compound anti-aging agent, is used to prepare the chloroprene rubber with stability.Its weak point is that anti ageing property is undesirable, and BHT has the detrimentally affect to environment.
Rubber World, 2006,234 (5): 22-27. discloses the using method of antideteriorant BHT in rubber, because little, the high volatility of molar mass of BHT, diffusive migration vapors away then to the surface from rubber easily.Finally make the oxidation inhibitor approach exhaustion in the polymkeric substance, therefore, think that the anti-aging usefulness of BHT reduces, it is long-lasting to lack.
Agric.Food Chem, 2007,55 (8): 3225-3231. discloses BHT and anti-aging agent 2, diffusive migration performance, the volatilization loss situation of 2 '-methylene bis (the 4-tertiary butyl-6-methylphenol) (2246) in polymkeric substance.The result is conspicuous, has further confirmed the easy migration volatility of BHT.Show that thus temperature and molar mass play conclusive effect to travelling speed.Temperature increases, and rate of migration strengthens; Molar mass increases, and rate of migration reduces.Use BHT as the main unfavorable factor of anti-aging agent to be in the synthetic rubber: when being heated, BHT diffusion mobility from rubber enters into environment then to the surface, cause environmental pollution.
Initial Assessment Report.Paris, March 2002:1-33. report, under natural environmental condition, BHT is difficult for biological degradation takes place, and can decompose some kinds of metabolites rapidly.In common atmospheric moisture, oxygen level, water quality and soil microorganisms effect only have 25% not change down to Mikami et al with spectroscopic analysis research BHT, and 24.8% of remainder can be decomposed into its homologue at short notice; 48% is unascertainable toxic chemical substance metabolite.
Chem.Res.Toxicol, 2007,20 (2): 199-207.B.W.Meier etc. are to the research of mutagenicity, and the chronic poisoning data that long-term experimentation on animals obtains show: the toxic chemical substance metabolite will cause transgenation, cell proliferation and tumour accelerating effect that the persistence contact causes.
Add BHT in the chloroprene rubber, inevitably ecotope and human health are caused certain harm.Bisphenolmonoacryates oxidation inhibitor contains two phenyl ring, and molecular weight is more than the twice of BHT, the boiling point height, and volatility is low, and good stability in polymkeric substance is difficult for diffusive migration; Partition ratio (being called for short the LogKow value) 7.46-13.10, BHT is 5.1, toxicity is little more a lot of than BHT.
Bisphenolmonoacryates oxidation inhibitor.Be the carbonium ion trapping agent, have the irreplaceable attribute of traditional alkylphenol oxidation inhibitor.Stabilizing mechanism as antioxidant of bisphenol mono acrylic ester GS:
As shown in the figure, polymkeric substance (RH) loses a proton under aging condition, generates alkyl diradical (R).The further oxidized generation peroxy radical of alkyl diradical (ROO), peroxy radical are captured the hydrogen atom in the polymkeric substance (RH) again, form new (R) and hydroperoxide (ROOH) again.The automatic promote the oxidation of polymkeric substance takes place in so circulation.The stabilizing mechanism of GS is that the two bond energys on the intramolecularly acryl are enough caught the alkyl diradical R that produces in the polymkeric substance (step 1) is made it to be attached on two keys in the conjugation mode, forms enol type free base (step 2).And the intramolecular hydrogen bond of ketonic oxygen and hydroxyl closes, and makes the hydrogen transference of the very fast generation intramolecularly of enol type free base again, generates stable phenol oxyradical (step 3).
The interaction of two special efficacy functional groups in the diphenyl acrylate has the special usefulness of catching R, in the initial root that just can cut off chainpropagation of rubber polymer generation autoxidation, has prevented that alkyl diradical from further wearing out with the oxygen reaction.Yet it and Hinered phenols primary antioxidant, thioether class auxiliary antioxidant be composite perfectly effect is arranged, because the Hinered phenols primary antioxidant can in time be caught the peroxy radical that produces in the rubber, thioether class auxiliary antioxidant can in time decompose the hydroperoxide that produce in the rubber, oxidation inhibitor synergy with three kinds of difference in functionalitys is to the bigger effect of anti-aging generation of rubber.
1%, the 5% thermal weight loss temperature of BHT is 100 ℃ and 135 ℃, shows to be easy to take place thermolysis or volatilization loss.Rubber is producing, in the course of processing, through the higher unit process of excess temperature, making that the antioxidant BHT effective content of poor heat stability reduces in the sizing material, and is undisputed, causes the anti ageing property of rubber product when storing to reduce.In addition, antioxidant product and thermal decomposition product enter into production environment, are difficult to avoid operator's the suction injury or the pollution of surrounding enviroment.
Studies show that, it is raw material that the present invention adopts bisphenolmonoacryates oxidation inhibitor and Hinered phenols antioxidant and thioether oxidation inhibitor, the ternary composite antioxidant of making uses in synthetic chloroprene rubber, having that product Heat stability is good, anti-oxidant efficient height, consumption are few, the characteristics of environmental protection, is that antideteriorant BHT is incomparable.
The present invention is directed in the chloroprene rubber production process add the antideteriorant BHT anti ageing property poor, environmental pollution problems arranged, effective choice contains the ternary complex antiager of bisphenolmonoacryates anti-aging agent, research its preparation method and service regulations, obtain a kind of chloroprene rubber product with stability, the continuation that is intended to improve anti ageing property, eliminate disporduct BHT is used.
Summary of the invention
The present invention seeks in order to overcome chloroprene rubber anti-aging agent deficiency of the prior art, by a kind of bisphenolmonoacryates anti-aging agent, a kind of Hinered phenols anti-aging agent and a kind of thioether anti-aging agent is raw material, carry out compositely according to the proportioning of regulation, mix, make ternary complex antiager; Under the room temperature,, add emulsifier aqueous solution then and mix fully, make ternary composite type anti-aging agent emulsion after the dispersion the ternary complex antiager organic solvent dissolution.
The present invention prepares in the ternary composite type anti-aging agent process, and the mass ratio of bisphenolmonoacryates anti-aging agent and Hinered phenols anti-aging agent and three kinds of materials of thioether class anti-aging agent is 1: 1～5: 1～5, and suitable mass ratio is 1: 1～3: 1～3.
Wherein the present invention prepares and adopts the bisphenolmonoacryates anti-aging agent of stating in the compound anti-aging agent process and be:
2-[1-(2-hydroxyl-3,5-di-tert-butyl-phenyl)-methyl]-4,6-di-tert-butyl-phenyl acrylate (be called for short: MA), chemical structural formula is as follows:
2-[1-(2-hydroxyl-3,5-two tertiary amyl phenyl)-ethyl]-4,6-two tertiary amyl phenyl acrylate (are called for short: GS);
2-tertiary butyl-6-(3-tertiary butyl-2-hydroxy-5-methyl base phenyl)-4-methylphenol acrylate (is called for short: GM).
Described Hinered phenols anti-aging agent is:
2,2 '-methylene-bis (4, the 6-DI-tert-butylphenol compounds) (is called for short: 2246-A);
2,2 '-ethylene two (4,6-two tert-amyl phenols) (is called for short: 2246-B);
2,2 '-ethylene two (4, the 6-DI-tert-butylphenol compounds) (is called for short: 2246-C);
B-(4-hydroxyl-3,5-di-tert-butyl-phenyl) the positive octadecyl ester of propionic acid;
Four (β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester;
Three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester;
Two (2, the 4-di-tert-butyl-phenyl) pentaerythritol diphosphites (is called for short: 626).
Described thioether class anti-aging agent is:
Methylene bis (dodecyl sulfide) (be called for short: methene-S-S-12), chemical structural formula is as follows:
H
25C
12S-CH
2-SC
12H
25
2,2 '-sulfurous ethyl glycol two (β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester);
Two (3, the 5-di-tert-butyl-4-hydroxyl benzyl) thioether (be called for short: methene-4426-S);
4,4 ' thiobiss (2-methyl-6-tert butyl phenol);
2,2 ' thiobiss (4-methyl-6-tert butyl phenol);
4,4 ' thiobiss (2,6 di t butyl phenol);
4,4 ' thiobiss (6-tertiary butyl meta-cresol);
Tyox B;
Thio-2 acid two (18) ester;
Thio-2 acid two (14) ester.
The present invention prepares in the ternary complex antiager emulsion process, and the organic solvent that is used to dissolve the ternary composite type anti-aging agent is benzene, toluene or dimethylbenzene.The mass ratio of ternary composite type anti-aging agent and organic solvent is 1: 2.
The present invention prepares in the ternary complex antiager emulsion process, the emulsifying agent that adopts is the mixture of the disproportionated rosin acid soap aqueous solution and the sulfonic acid analog anion surfactants aqueous solution, wherein the disproportionated rosin acid soap aqueous solution is the commercially available nilox resin acid potash soap aqueous solution or the nilox resin acid soda soap aqueous solution, the massfraction of the disproportionated rosin acid soap aqueous solution is 10%, and the massfraction of water is 90%; Sulfonic acid analog anion surfactants refers to alkyl sodium sulfonate, sodium alkyl benzene sulfonate, petroleum sodium sulfonate, sodium naphthalene sulfonate, sodium alkyl naphthalene sulfonate, and the massfraction of sulfonic acid analog anion surfactants is 23%, and the massfraction of water is 77%.Add a kind of bisphenolmonoacryates anti-aging agent and a kind of Hinered phenols anti-aging agent and a kind of thioether anti-aging agent, organic solvent in the mixing tank in proportion, normal temperature stirs down and makes it to dissolve fully, add massfraction more in proportion and be 10% the nilox resin acid potash soap aqueous solution, massfraction in mixing tank and be 23% the sulfonic acid analog anion surfactants aqueous solution, wherein the mass ratio of the sour potash soap aqueous solution of ternary complex antiager and nilox resin and sodium dodecyl benzene sulfonate aqueous solution is 1: 0.67: 0.67; After high-speed stirring is carried out thorough mixing, obtain the ternary complex antiager emulsion, wherein the massfraction of ternary complex antiager is 23.1% in the ternary composite type anti-aging agent emulsion.
The ternary complex antiager emulsion is added in the chloroprene rubber latex that adopts emulsion polymerization production, dry glue quality meter according to chloroprene rubber adds the ternary complex antiager emulsion, and the mass ratio of the dry glue quality of chloroprene rubber and ternary complex antiager emulsion is: 1: 0.03～0.07
The chloroprene rubber latex that the present invention uses refers to 2-chloro-1, the 3-divinyl is a polymerization single polymerization monomer, water is dispersion medium, disproportionated rosin soaps etc. are emulsifying agent, lauryl mercaptan or thiuram are molecular weight regulator, the chloroprene rubber latex that adopts emulsion polymerization to produce, company limited produces by the long-lived chemical industry in Sichuan.
The present invention adds the ternary complex antiager emulsion in chloroprene rubber latex, after the chloroprene rubber latex that adds the ternary complex antiager emulsion fully stirred, mixes, obtain containing the chloroprene rubber latex of ternary complex antiager emulsion, through obtaining a kind of synthetic chloroprene rubber product after cohesion, washing, the drying with stability.
Mensuration has the ageing resistance of the synthetic chloroprene rubber product of stability.
The advantage that the present invention has:
1, to adopt bisphenolmonoacryates anti-aging agent and Hinered phenols anti-aging agent and thioether anti-aging agent be raw material in the present invention, the ternary complex antiager of making uses in synthetic chloroprene rubber, has that product Heat stability is good, anti-oxidant efficient height, consumption are few, the characteristics of environmental protection.
2, studies show that at senile experiment: added the chloroprene rubber product that ternary complex antiager emulsion of the present invention is made, in weathering process, the intensity of variation of its rubber appearance color, Mooney viscosity, Mooney scorch time, mechanical strength performance index is significantly less than by using the made synthetic chloroprene rubber product of antideteriorant BHT.
3, the present invention prepares a kind of ternary complex antiager emulsion and the technological method used in synthetic chloroprene rubber, solves in traditional chloroprene rubber production process, and the problem that use antideteriorant BHT cause works the mischief to ecotope and human health,
Embodiment
1, select the bisphenolmonoacryates anti-aging agent of Jiangsu Polytechnic University's preparation for use: 2-[1-(2-hydroxyl-3, the 5-di-tert-butyl-phenyl)-and methyl]-4,6-di-tert-butyl-phenyl acrylate (is called for short: MA) or 2-[1-(2-hydroxyl-3,5-two tertiary amyl phenyl)-and ethyl]-4,6-two tertiary amyl phenyl acrylate (are called for short: GS), select for use Jiangsu Polytechnic University to prepare the Hinered phenols anti-aging agent: 2,2 '-ethylene two (4,6-two tert-amyl phenols) (be called for short: 2246-B), 2,2 '-ethylene two (4, the 6-DI-tert-butylphenol compounds) (is called for short: 2246-C), 2,2 '-methylene-bis (4, the 6-DI-tert-butylphenol compounds) (is called for short: 2246-A); Commercially available two (2, the 4-di-tert-butyl-phenyl) pentaerythritol diphosphites (is called for short: anti-aging agent 626); Select thioether class anti-aging agent for use with Jiangsu Polytechnic University's preparation: two (3, the 5-di-tert-butyl-4-hydroxyl benzyl) thioether (be called for short: methene-4426-S); Commercially available methylene bis (dodecyl sulfide) (be called for short: methene-S-S-12).
Select for use commercially available 2,6 di tert butyl 4 methyl phenol (to be called for short: antideteriorant BHT)
2, the CR244 model neoprene latex of selecting for use Sichuan long-lived chemical industry company limited to produce, dry glue quality mark 37.8%; CR322 model neoprene latex, dry glue quality mark 39.5%,
3, select commercially available industrial top grade product toluene for use, as the organic solvent of dissolved solids anti-aging agent; Select the commercially available industrial top grade product 10% nilox resin acid potash soap aqueous solution for use, commercially available industrial top grade product 23% sodium dodecyl benzene sulfonate aqueous solution is as the emulsifying agent raw material of preparation ternary complex antiager emulsion process.
4, the mass ratio of bis-phenol list acrylic acid or the like anti-aging agent and Hinered phenols anti-aging agent and three kinds of materials of thioether class anti-aging agent is 1: 1～3: 1～3.Composite, as to make 150 grams ternary complex antiager 1#～8#, the mass ratio of various anti-aging agent is as shown in table 1.
Table 1. ternary composite antioxidant is formed
5, in the beaker of 1000mL, add 1# in the 150 gram tables 1～8# ternary complex antiager respectively, 300 gram toluene, fully stirring makes it to dissolve fully.Then, add 100 grams, the 10% nilox resin acid potash soap aqueous solution, 100 grams, 23% sodium dodecyl benzene sulfonate aqueous solution.At 5000-7000 rev/min of thorough mixing, make 1#～8# ternary complex antiager emulsion with high-speed shearing machine respectively, the massfraction of ternary complex antiager is 23.1%.
6, in the beaker of 1000mL, add 150 gram antideteriorant BHTs, 300 gram toluene, fully stirring makes it to dissolve fully.Then, add 100 grams, the 10% nilox resin acid potash soap aqueous solution, 100 grams, 23% sodium dodecyl benzene sulfonate aqueous solution.At 5000-7000 rev/min of thorough mixing, form the finely dispersed emulsion of antideteriorant BHT with high-speed shearing machine, i.e. antideteriorant BHT emulsion, the massfraction of BHT is 23.1%.
7, in chloroprene rubber latex, add the ternary complex antiager emulsion in proportion, after thorough mixing is uniformly dispersed, condense.Condensing method: stir on the chloroprene rubber latex limit that will contain the ternary complex antiager emulsion, it is that 30～40% acetate and massfraction are 2～4% dispersion agent (Henkel chemical company limited product: LomarPW) mixed aqueous solution that the limit slowly drips massfraction, regulate latex PH to 6.0～6.5, make it be tiled into thin layer equably then, place in the freezer compartment of refrigerator, about-20 ℃, parked 30～35 minutes, make latex freeze agglomeration flakiness, the emulsifying agent of surface attachment is removed in washing, place baking oven, 105 ℃ of forced air dryings 30～35 minutes promptly get dried glue sample.
Embodiment 1
Take by weighing CR244 neoprene latex 3000 grams, 1# ternary complex antiager emulsion 46 grams fully mix.Obtain a kind of chloroprene rubber product after process cohesion, washing, the drying, i.e. the 1# sample with stability.
Embodiment 2
Take by weighing CR244 neoprene latex 3000 grams, 2# ternary complex antiager emulsion 26 grams fully mix.Obtain a kind of chloroprene rubber product after process cohesion, washing, the drying, i.e. the 2# sample with stability.
Embodiment 3
Take by weighing CR244 neoprene latex 3000 grams, 3# ternary complex antiager emulsion 76 grams fully mix.Obtain a kind of chloroprene rubber product after process cohesion, washing, the drying, i.e. the 3# sample with stability.
Embodiment 4
Take by weighing CR244 neoprene latex 3000 grams, 4# ternary composite antioxidant emulsion 48 grams fully mix.Obtain a kind of chloroprene rubber product after process cohesion, washing, the drying, i.e. the 4# sample with stability.
Embodiment 5
Take by weighing CR322 neoprene latex 3000 grams, 5# ternary composite antioxidant emulsion 50 grams fully mix.Obtain a kind of chloroprene rubber product after process cohesion, washing, the drying, i.e. the 5# sample with stability.
Embodiment 6
Take by weighing CR322 neoprene latex 3000 grams, 6# ternary composite antioxidant emulsion 40 grams fully mix.Obtain a kind of chloroprene rubber product after process cohesion, washing, the drying, i.e. the 6# sample with stability.
Embodiment 7
Take by weighing CR322 neoprene latex 3000 grams, 7# ternary composite antioxidant emulsion 45 grams fully mix.Obtain a kind of chloroprene rubber product after process cohesion, washing, the drying, i.e. the 7# sample with stability.
Embodiment 8
Take by weighing CR322 neoprene latex 3000 grams, 8# ternary composite antioxidant emulsion 48 grams fully mix.Obtain a kind of chloroprene rubber product after process cohesion, washing, the drying, i.e. the 8# sample with stability.
Comparative example 1
Take by weighing CR244 neoprene latex 3000 grams, 95 gram antideteriorant BHT emulsions fully mix.Obtain a kind of chloroprene rubber product after process cohesion, washing, the drying, i.e. the 9# sample with stability.
Comparative example 2
Take by weighing CR322 neoprene latex 3000 grams, 95 gram antideteriorant BHT emulsions fully mix.Obtain a kind of chloroprene rubber product after process cohesion, washing, the drying, i.e. the 10# sample with stability
Experimental technique
1, uses the TGA503 thermogravimetric analyzer, under nitrogen protection, with the temperature of 1# in the temperature rise rate test chart 1 of 20 ℃/min～8# ternary composite antioxidant, 9# antideteriorant BHT thermal weight loss 1% and 5%.
2, with DSC200PC type differential scanning calorimetric analysis instrument, get quality and place aluminum dish for 1#～8# sample, the 9# duplicate BR glue sample of (15.0 ± 0.5) mg, with the logical people's nitrogen of (50 ± 5) mL/min, 20 ℃/min of control temperature rise rate is warming up to 120 ℃.Constant temperature 3min uses replacement of oxygen nitrogen, and 120 ℃ of constant temperature appear as the oxidation induction period of glue sample up to the exothermic maximum signal.
3,1#～8# sample, 9# duplicate are made print, place the thermo-oxidative ageing case respectively, press GB/T 3512-1992, ℃ carry out thermo-oxidative ageing test, the time dependent degree of color of observing the glue sample in (70 ± 1).
4,1#～8# sample, 9# duplicate are made print, place the thermo-oxidative ageing case,, ℃ carry out the thermo-oxidative ageing test in (70 ± 1) according to GB/T 3512-1992, sample behind the thermo-oxidative ageing with automatic Mooney viscosity tester, is pressed the Mooney viscosity ML that GB/T1232-1992 measures the rubber sample
1+4 100 ℃
5, press the Mooney scorch time MS that GB/T1232-1992 measures the rubber unvulcanizate sample
1+4 120 ℃
6, press the mechanics tensile property of GB/T15257-94, GB/T528-1992 test rubber unvulcanizate sample.
Experimental result
The temperature of table 2, ternary complex antiager and BHT thermal weight loss 1% and 5%
| Numbering | 1% weightless temperature | 5% weightless temperature | Numbering | 1% weightless temperature | 5% weightless temperature |
| ??1# ??2# ??3# ??4# ??5# | ?208℃ ?211℃ ?215℃ ?201℃ ?213℃ | ?238℃ ?243℃ ?251℃ ?237℃ ?249℃ | ??6# ??7# ??8# ??9# ??10# | ?216℃ ?206℃ ?210℃ ?100℃ ?100℃ | ?248℃ ?233℃ ?240℃ ?135℃ ?135℃ |
Table 3, CR244, CR322 chloroprene rubber product sample are at 120 ℃ oxidation induction period
| Numbering | CR244 glue sample oxidation induction period (min) | Numbering | CR322 glue sample oxidation induction period (min) |
| ??1# ??2# ??3# ??4# ??9# | ??146 ??140 ??143 ??145 ??61 | ??5# ??6# ??7# ??8# ??10# | ??159 ??161 ??156 ??152 ??70 |
Table 4,70 ℃ of thermo-oxidative ageing tests, CR244 chloroprene rubber product sample appearance color changes
Table 5,70 ℃ of thermo-oxidative ageing tests, CR322 chloroprene rubber product sample appearance color changes
Table 6,70 ℃ of thermo-oxidative ageing tests, CR244 chloroprene rubber product sample Mooney viscosity ML
1+4 100 ℃Variation
Table 7,70 ℃ of thermo-oxidative ageing tests, CR322 chloroprene rubber product sample Mooney viscosity ML
1+4 100 ℃Variation
Table 8,70 ℃ of thermo-oxidative ageing tests, CR322 chloroprene rubber product sample mooney scorch MS
1+4 120 ℃(min) variation
Table 9,70 ℃ of thermo-oxidative ageing tests, the variation of CR322 chloroprene rubber product rubber unvulcanizate sample tensile strength (MPa)
Table 10,70 ℃ of thermo-oxidative ageing tests, the variation of CR322 chloroprene rubber product rubber unvulcanizate sample tensile yield (%)
Table 11,70 ℃ of thermo-oxidative ageing tests, the variation of CR322 chloroprene rubber product rubber unvulcanizate sample tension set (%)
Table 12,70 ℃ of thermo-oxidative ageing tests, the variation of CR322 chloroprene rubber product rubber unvulcanizate sample 500% stress at definite elongation (MPa)
Senile experiment is the result show, compare with the chloroprene rubber product that uses traditional antideteriorant BHT to make by the chloroprene rubber product that ternary complex antiager emulsion of the present invention is made, in weathering process, performance index such as its rubber appearance color, Mooney viscosity, Mooney scorch time, mechanical strength are significantly less than by the made synthetic chloroprene rubber product of antideteriorant BHT.Illustrate that the ternary complex antiager of the present invention's preparation can improve the stability of chloroprene rubber product.
Claims (7)
1, the manufacture method of ternary complex antiager is a raw material by a kind of bisphenolmonoacryates anti-aging agent, a kind of Hinered phenols anti-aging agent and a kind of thioether anti-aging agent, carries out compositely according to the proportioning of regulation, mixes, and makes ternary complex antiager; The mass ratio that it is characterized in that bisphenolmonoacryates anti-aging agent and Hinered phenols anti-aging agent and three kinds of materials of thioether class anti-aging agent is 1: 1～5: 1～5.
2, the manufacture method of ternary complex antiager according to claim 1 is characterized in that the mass ratio of described bisphenolmonoacryates anti-aging agent and Hinered phenols anti-aging agent and three kinds of materials of thioether class anti-aging agent is 1: 1～3: 1～3.
3, the manufacture method of ternary complex antiager emulsion, under the room temperature, will be according to the ternary complex antiager organic solvent dissolution of the described method preparation of claim 1, add the disproportionated rosin acid soap aqueous solution then and mix fully, make ternary composite type anti-aging agent emulsion after the dispersion with the emulsifying agent that the mixture of the sulfonic acid analog anion surfactants aqueous solution is made; The mass ratio that it is characterized in that ternary complex antiager and organic solvent is 1: 2; The mass ratio of ternary complex antiager and the nilox resin acid potash soap aqueous solution and sodium dodecyl benzene sulfonate aqueous solution is 1: 0.67: 0.67.
4, the manufacture method of ternary complex antiager emulsion according to claim 3 is characterized in that described organic solvent is benzene, toluene or dimethylbenzene; The massfraction of the described nilox resin acid potash soap aqueous solution is 10%; The massfraction of described sodium dodecyl benzene sulfonate aqueous solution is 23%.
5, the manufacture method of the described ternary complex antiager emulsion of the manufacture method of ternary complex antiager according to claim 1 or claim 3, it is characterized in that described bisphenolmonoacryates anti-aging agent is: 2-[1-(2-hydroxyl-3, the 5-di-tert-butyl-phenyl)-and methyl]-4,6-di-tert-butyl-phenyl acrylate or 2-[1-(2-hydroxyl-3,5-two tertiary amyl phenyl)-and ethyl]-4,6-two tertiary amyl phenyl acrylate or 2-tertiary butyl-6-(3-tertiary butyl-2-hydroxy-5-methyl base phenyl)-4-methylphenol acrylate; Described Hinered phenols anti-aging agent is: 2, and 2 '-methylene-bis (4, the 6-DI-tert-butylphenol compounds) or 2,2 '-ethylene two (4,6-two tert-amyl phenols) or 2,2 '-ethylene two (4, the 6-DI-tert-butylphenol compounds) or two (2, the 4-di-tert-butyl-phenyl) pentaerythritol diphosphites; Described thioether class anti-aging agent is: methylene bis (dodecyl sulfide) (is that methene-S-S-12) or two (3, the 5-di-tert-butyl-4-hydroxyl benzyl) thioether (are methene-4426-S).
6, the manufacture method of ternary complex antiager emulsion according to claim 3, the massfraction that it is characterized in that ternary complex antiager in the ternary complex antiager emulsion is 23.1%.
7, ternary complex antiager, emulsion are used in chloroprene rubber, it is characterized in that in synthetic chloroprene rubber latex, dry glue quality meter according to chloroprene rubber adds the ternary complex antiager emulsion, and the mass ratio of the dry glue quality of chloroprene rubber and ternary complex antiager emulsion is: 1: 0.03～0.07.
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