CN105602022B - A kind of preparation method of phenol measure standard rubbers sample - Google Patents
A kind of preparation method of phenol measure standard rubbers sample Download PDFInfo
- Publication number
- CN105602022B CN105602022B CN201610064424.3A CN201610064424A CN105602022B CN 105602022 B CN105602022 B CN 105602022B CN 201610064424 A CN201610064424 A CN 201610064424A CN 105602022 B CN105602022 B CN 105602022B
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- China
- Prior art keywords
- phenol
- rubber
- sample
- preparation
- kneaded
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N2001/2893—Preparing calibration standards
Abstract
The present invention provides a kind of preparation method of phenol measure standard rubbers sample, in rubber after the additions such as target compound phenol, solid softener, filler, age resistor and accelerator are plasticated, then it is kneaded in banbury, then extruded and vulcanizing treatment, and the rubber product is carried out after series of processes to obtain standard sample.The present invention obtains phenol measure standard sample by preparation method simple to operate, is favorably improved the comparativity and uniformity of laboratory monitoring detection data, is laid a good foundation for the unified standard detected, provides possibility.
Description
【Technical field】
The present invention relates to a kind of preparation method of phenol measure standard rubbers sample.
【Background technology】
Phenol is important basic organic chemical industry raw material, and its many downstream product is related to various fields, industrially
Have many uses, mainly for the manufacture of phenolic resin, bisphenol-A and caprolactam.In rubber industry, aldehydes matter is mainly as anti-
Old agent, individual plants have the function that certain resistance valence metal ion catalysis oxidation.Its advantage is non-polluting, suitable for shallow
Color rubber；And solubility of the phenol antiager in rubber is higher, in the absence of bloom problem.
Phenol has strong corrosiveness to skin, mucous membrane, can suppress nervous centralis or infringement Liver and kidney function.Phenol can
Cause headache, dizziness, cough, anorexia, Nausea and vomiting, severe patient causes albuminuria, can cause dermatitis.High concentration is sucked to steam
Gas can cause headache, dizzy, weak, blurred vision, pulmonary edema etc..Wrongly take and cause alimentary canal to be burnt, burning pain, expiratory air band occur
Phenol taste, vomitus or the possibility that with blood, can have gastric-intestinal perforation greatly, may occur in which shock, pulmonary edema, liver or renal damage, occur
Acute renal failure, respiratory failure can be died from.Such material of the numerous and confused statute restrictions system of the states such as European Union, the U.S..European Union provides
The maximum acceptable migration amount of product phenol for directly contacting food be 0.05mg/l, and maximum concentration, which is limited the quantity, in air is
0.003mg/m3.Provide that phenol migration limitation is 15mg/l in 88/378/EEC instructions.The U.S. using phenol as the fourth stage (altogether
12 grades) harmful substance.Most of toys and footwear contain rubber constituent, and the phenol problem in rubber has caused the wide of society
General pass.
The assay method of phenol is mainly liquid chromatography in rubber at present, and other standard methods are also among research.
Develop in rubber phenol measure standard sample for improve footwear, toy and articles for children manufacturing enterprise and supervision department and
The detection level in social third party laboratory, it is particularly significant to ensure that footwear, toy and articles for children quality safety etc. have
Meaning.
【The content of the invention】
The technical problem to be solved in the present invention, it is to provide a kind of preparation method of phenol measure standard rubbers sample,
It is favorably improved the comparativity and uniformity of phenol detection data in laboratory monitoring rubber, and phenol in rubber is detected to be unified
Standard is laid a good foundation, and also has the characteristics of simple and convenient, workable.
What the present invention was realized in：
A kind of preparation method of phenol measure standard rubbers sample, the preparation method step are as follows：
Step 1: rubber is plasticated, 3~10h is parked in then cooling；When being plasticated using mill, plasticating temperature
Scope is 30 DEG C~70 DEG C, and the time is 5min~20min；When being plasticated using banbury, temperature is 90 DEG C~120 DEG C, the time
For 2min~8min；
Step 2: two sections are kneaded method and are kneaded, following component raw material is added in banbury at a slow speed：Rubber mass percent is
4%~10% solid softener, 40%~80% filler, 1%~4% age resistor, accelerator 6%~10%, 0.02%
~0.30% phenol, is kneaded 2min~10min, and temperature is no more than 100 DEG C；
Then the filler of rubber mass percent 10%~20% is added in the sample after above-mentioned mixing again, 1%~2% promotees
Enter agent, be kneaded 1min~10min, temperature is no more than 130 DEG C；Then discharge cools down, and parks 10h~36h；
It is preheated to Step 3: being kneaded uniform heel row and expecting in 140 DEG C~165 DEG C moulds, is placed in applying pressure on purl machine
Power, at least 3.5MPa is slowly pressurized to, extruded 3~5 times, after temperature is reduced to below 100 DEG C, add vulcanizing agent 3%
~5%, vulcanize 5min~25min, thickness is more than 0.6cm during vulcanization, and then progress extrusion technique operation, makes glue by extruder
For material in flake, thickness is 0.3cm~0.5cm, cooling, produces crude samples；By the uneven part house of the peripheral thickness of crude samples
Abandon, only stay interior thickness uniform parts, be cooled to room temperature afterwards, and wrapped with hermetic bag, as standard sample.
Further, described matrix material rubber is natural rubber, butadiene-styrene rubber, neoprene, EP rubbers and butyronitrile
At least one of rubber.
Further, the coefficient of the banbury in the step 1 and step 2 is 0.50~0.75, rotor speed
For 40~60r/min.
Further, 1cm parts in crude samples periphery are given up in the step 3.
Further, the solid softener is at least one of paraffin, stearic acid, lignite wax；Filler is white carbon
At least one of black, magnesia, zinc oxide, titanium oxide, calcium hydroxide, calcium carbonate, talcum powder, carbon black and graphite powder；Promote
Agent is aminodithioformic acid rare-earth salts, accelerator TP, accelerator PZ, captax, altax, in accelerator PX at least
It is a kind of；Age resistor is antioxidant 2246, antioxidant D FC-34, antioxidant 4010NA, antioxidant 4020, antioxidant DBH, age resistor
At least one of A；Vulcanizing agent is at least one in sulphur, vulcanizing agent DTDM, paraquinonedioxime, vulcanizing agent DBQD, vulcanizing agent DCP
Kind.
The invention has the advantages that：
Rubber is obtained by the preparation method of the present invention and determines phenol standard sample, is favorably improved laboratory monitoring rubber
The comparativity and uniformity of middle adjacent phenol detection data, lay a good foundation for the unified standard for detecting phenol in rubber, provide
May；In addition, the preparation method of the present invention has the characteristics of simple and convenient, workable.
【Embodiment】
A kind of phenol measure preparation method of standard rubbers sample involved in the present invention, the preparation method step is such as
Under：
Step 1: rubber is plasticated, 3~10h is parked in then cooling；When being plasticated using mill, plasticating temperature
Scope is 30 DEG C~70 DEG C, and the time is 5min~20min；When being plasticated using banbury, temperature is 90 DEG C~120 DEG C, the time
For 2min~8min；
Step 2: two sections are kneaded method and are kneaded, following component raw material is added in banbury at a slow speed：Rubber mass percent is
4%~10% solid softener, 40%~80% filler, 1%~4% age resistor, accelerator 6%~10%, 0.02%
~0.30% phenol, is kneaded 2min~10min, and temperature is no more than 100 DEG C；Then life is added in the sample after above-mentioned mixing again
The filler of glue mass percent 10%~20%, 1%~2% accelerator are kneaded 1min~10min, and temperature is no more than 130 DEG C；
Then discharge cools down, and parks 10h~36h；
It is preheated to Step 3: being kneaded uniform heel row and expecting in 140 DEG C~165 DEG C moulds, is placed in applying pressure on purl machine
Power, at least 3.5MPa is slowly pressurized to, extruded 3~5 times, after temperature is reduced to below 100 DEG C, add vulcanizing agent 3%
~5%, vulcanize 5min~25min, thickness is more than 0.6cm during vulcanization, and then progress extrusion technique operation, makes glue by extruder
For material in flake, thickness is 0.3cm~0.5cm, cooling, produces crude samples；By the uneven part house of the peripheral thickness of crude samples
Abandon, only stay interior thickness uniform parts, be cooled to room temperature afterwards, and wrapped with hermetic bag, as standard sample.
Described matrix material rubber be natural rubber, butadiene-styrene rubber, neoprene, EP rubbers and nitrile rubber in extremely
Few one kind.The coefficient of banbury in the step 1 and step 2 is 0.50~0.75, and rotor speed is 40~60r/
min。
1cm parts in crude samples periphery are given up in the step 3.
The solid softener is at least one of paraffin, stearic acid, lignite wax；Filler be White Carbon black, magnesia,
At least one of zinc oxide, titanium oxide, calcium hydroxide, calcium carbonate, talcum powder, carbon black and graphite powder；Accelerator is two thio
Carbamic acid rare-earth salts, accelerator TP, accelerator PZ, captax, at least one of altax, accelerator PX；Age resistor
For antioxidant 2246, at least one in antioxidant D FC-34, antioxidant 4010NA, antioxidant 4020, antioxidant DBH, antioxidant A
Kind；Vulcanizing agent is at least one of sulphur, vulcanizing agent DTDM, paraquinonedioxime, vulcanizing agent DBQD, vulcanizing agent DCP.
In order to which preferably the present invention will be described, the present invention is for following several embodiments.
Embodiment one
The content for preparing phenol accounts for the standard sample of standard specimen supplementary material gross weight 0.010%：
Natural rubber 1kg, is plasticated using mill, and plasticating temperature is 55 DEG C, and plasticate 15min, and 8h is parked in then cooling.
The rubber added in mill after plasticating, 50g paraffin, 450g White Carbon blacks, 50g zinc oxide, 15g antioxidant Ds FC-34,15g antioxygen
Agent 2246,60g captaxs, 24g phenol, temperature are 55 DEG C, are kneaded 5min；Then 200g White Carbon blacks are added, 10g zinc oxide,
110g captaxs, are kneaded 3min, and temperature is 60 DEG C.Then discharge cools down, and parks 24h.It is kneaded uniform heel row and expects and is preheated to
In 140 DEG C of moulds, it is placed in applying pressure on purl machine, is slowly pressurized to as 3.5MPa, extrudes 3 times, treat that temperature is reduced to 95
DEG C when, add 30g vulcanizing agent DBQD, vulcanize 15min, thickness position 0.8cm during vulcanization.Then extrusion technique operation is carried out, is passed through
Extruder makes sizing material, and in flake, thickness is about 0.5cm, cooling.The periphery 1cm parts of the sample are given up, and only stay center section,
Sample is cooled to room temperature afterwards, the center section wrapped with hermetic bag, the part remained is standard sample.
Embodiment two
The content for preparing phenol accounts for the standard sample of standard specimen supplementary material gross weight 0.050% respectively：
Natural rubber 1kg, is plasticated using mill, and plasticating temperature is 55 DEG C, and plasticate 15min, and 8h is parked in then cooling.
The rubber added in mill after plasticating, 50g paraffin, 450g White Carbon blacks, 50g zinc oxide, 15g antioxidant Ds FC-34,15g antioxygen
Agent 2246,60g captaxs, 55g phenol, temperature are 55 DEG C, are kneaded 5min；Then 200g White Carbon blacks are added, 10g zinc oxide,
110g captaxs, are kneaded 3min, and temperature is 60 DEG C.Then discharge cools down, and parks 24h.It is kneaded uniform heel row and expects and is preheated to
In 140 DEG C of moulds, it is placed in applying pressure on purl machine, is slowly pressurized to as 3.5MPa, extrudes 3 times, treat that temperature is reduced to 95
DEG C when, add 30g vulcanizing agent DBQD, vulcanize 15min, thickness position 0.8cm during vulcanization.Then extrusion technique operation is carried out, is passed through
Extruder makes sizing material, and in flake, thickness is about 0.5cm, cooling.The periphery 1cm parts of the sample are given up, and only stay center section,
Sample is cooled to room temperature afterwards, the center section wrapped with hermetic bag, the part remained is standard sample.
Embodiment three
The content for preparing phenol accounts for the standard sample of standard specimen supplementary material gross weight 0.100% respectively：
Natural rubber 1kg, is plasticated using mill, and plasticating temperature is 55 DEG C, and plasticate 15min, and 8h is parked in then cooling.
The rubber added in mill after plasticating, 50g paraffin, 450g White Carbon blacks, 50g zinc oxide, 15g antioxidant Ds FC-34,15g antioxygen
Agent 2246,60g captaxs, 110g phenol, temperature are 55 DEG C, are kneaded 5min；Then 200g White Carbon blacks, 10g oxidations are added
Zinc, 110g captaxs are kneaded 3min, and temperature is 60 DEG C.Then discharge cools down, and parks 24h.It is kneaded uniform heel row and expects preheating
Into 140 DEG C of moulds, it is placed in applying pressure on purl machine, is slowly pressurized to as 3.5MPa, extrudes 3 times, treat that temperature is reduced to
At 95 DEG C, 30g vulcanizing agent DBQD are added, vulcanize 15min, thickness position 0.8cm during vulcanization.Then extrusion technique operation is carried out, is led to
Crossing extruder makes sizing material be in flake, and thickness is about 0.5cm, cooling.The periphery 1cm parts of the sample are given up, and only stay pars intermedia
Point, sample is cooled to room temperature afterwards, the center section wrapped with hermetic bag, the part remained is standard sample
Product.
The standard sample that the various embodiments described above are obtained is respectively according to the series standards of GB/T 15000, using GB/T
22048-2008 detection methods carry out uniformity test and stability test, wherein：Uniformity test is using single-factor variance point
Analysis method (F methods), experiment show that the F values of made standard sample are respectively less than critical value Fα(f1, f2) (wherein α=0.05, f1=14, f2
=30), that is, show that made standard sample is uniform；Stability test uses " average value consistency check " side in t methods of inspection
Method, the interval time in checkout procedure are 10 days, 1 month, 6 months, 12 months, and experiment draws the t values of made standard sample
Less than critical value t α (n1+n2-2) (wherein α=0.05, n1=45, n2=10), that is, it is stable to show made standard sample.
To sum up, rubber is obtained by the preparation method of the present invention and determines rubber measure phenol standard sample, help to carry
The comparativity and uniformity of adjacent phenol detection data, are established for the unified standard for detecting phenol in rubber in high laboratory monitoring rubber
Basis, provide possibility；In addition, the preparation method of the present invention has the characteristics of simple and convenient, workable.
Although the foregoing describing the embodiment of the present invention, those familiar with the art should manage
Solution, the specific embodiment described by us are merely exemplary, rather than for the restriction to the scope of the present invention, are familiar with this
The equivalent modification and change that the technical staff in field is made in the spirit according to the present invention, should all cover the present invention's
In scope of the claimed protection.
Claims (5)
- A kind of 1. preparation method of phenol measure standard rubbers sample, it is characterised in that：The preparation method step is as follows：Step 1: rubber is plasticated, 3~10h is parked in then cooling；When being plasticated using mill, plasticating temperature scope For 30 DEG C~70 DEG C, the time is 5min~20min；When being plasticated using banbury, temperature is 90 DEG C~120 DEG C, and the time is 2min~8min；Step 2: two sections are kneaded method and are kneaded, following component raw material is added in banbury at a slow speed：Rubber mass percent is 4% ~10% solid softener, 40%~80% filler, 1%~4% age resistor, accelerator 6%~10%, 0.02%~ 0.30% phenol, is kneaded 2min~10min, and temperature is no more than 100 DEG C；Then the filler of rubber mass percent 10%~20% is added in the sample after above-mentioned mixing again, 1%~2% promotes Agent, is kneaded 1min~10min, and temperature is no more than 130 DEG C；Then discharge cools down, and parks 10h~36h；It is preheated to Step 3: being kneaded uniform heel row and expecting in 140 DEG C~165 DEG C moulds, is placed in applying pressure on purl machine, is delayed It is slow to be pressurized at least 3.5MPa, extrude 3~5 times, after temperature is reduced to below 100 DEG C, add vulcanizing agent 3%~5%, Vulcanize 5min~25min, thickness is more than 0.6cm during vulcanization, then carries out extrusion technique operation, makes sizing material be in thin by extruder Sheet, thickness are 0.3cm~0.5cm, cooling, produce crude samples；The uneven part of the peripheral thickness of crude samples is given up, only stayed Interior thickness uniform parts, room temperature is cooled to afterwards, and is wrapped with hermetic bag, as standard sample.
- A kind of 2. preparation method of phenol measure standard rubbers sample as claimed in claim 1, it is characterised in that：The base Body material rubber is at least one of natural rubber, butadiene-styrene rubber, neoprene, EP rubbers and nitrile rubber.
- A kind of 3. preparation method of phenol measure standard rubbers sample as claimed in claim 1, it is characterised in that：The step Rapid one and the banbury in step 2 coefficient be 0.50~0.75, rotor speed is 40~60r/min.
- A kind of 4. preparation method of phenol measure standard rubbers sample as claimed in claim 1, it is characterised in that：The step 1cm parts in crude samples periphery are given up in rapid three.
- A kind of 5. preparation method of phenol measure standard rubbers sample as claimed in claim 1, it is characterised in that：It is described solid Body softening agent is at least one of paraffin, stearic acid, lignite wax；Filler be White Carbon black, magnesia, zinc oxide, titanium oxide, At least one of calcium hydroxide, calcium carbonate, talcum powder, carbon black and graphite powder；Accelerator be aminodithioformic acid rare-earth salts, Accelerator TP, accelerator PZ, captax, at least one of altax, accelerator PX；Age resistor is antioxidant 2246, is prevented At least one of old agent DFC-34, antioxidant 4010NA, antioxidant 4020, antioxidant DBH, antioxidant A；Vulcanizing agent is sulphur At least one of sulphur, vulcanizing agent DTDM, paraquinonedioxime, vulcanizing agent DBQD, vulcanizing agent DCP.
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| CN201610064424.3A CN105602022B (en) | 2016-01-29 | 2016-01-29 | A kind of preparation method of phenol measure standard rubbers sample |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610064424.3A CN105602022B (en) | 2016-01-29 | 2016-01-29 | A kind of preparation method of phenol measure standard rubbers sample |
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| CN105602022B true CN105602022B (en) | 2018-03-23 |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102344624A (en) * | 2011-06-30 | 2012-02-08 | 福建出入境检验检疫局检验检疫技术中心 | Preparation method of standard sample for testing phthalic ester plasticizer |
| CN103642134A (en) * | 2013-11-12 | 2014-03-19 | 铜陵市肆得科技有限责任公司 | Combined rubber gasket material and preparation method thereof |
| WO2015101599A1 (en) * | 2013-12-30 | 2015-07-09 | Lanxess Deutschland Gmbh | Phenol-containing hydrogenated nitrile rubber |
-
2016
- 2016-01-29 CN CN201610064424.3A patent/CN105602022B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102344624A (en) * | 2011-06-30 | 2012-02-08 | 福建出入境检验检疫局检验检疫技术中心 | Preparation method of standard sample for testing phthalic ester plasticizer |
| CN103642134A (en) * | 2013-11-12 | 2014-03-19 | 铜陵市肆得科技有限责任公司 | Combined rubber gasket material and preparation method thereof |
| WO2015101599A1 (en) * | 2013-12-30 | 2015-07-09 | Lanxess Deutschland Gmbh | Phenol-containing hydrogenated nitrile rubber |
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| CN105602022A (en) | 2016-05-25 |
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