CN108218700A - A kind of automotive upholstery specialty plasticiser TM8 - Google Patents
A kind of automotive upholstery specialty plasticiser TM8 Download PDFInfo
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- CN108218700A CN108218700A CN201810079100.6A CN201810079100A CN108218700A CN 108218700 A CN108218700 A CN 108218700A CN 201810079100 A CN201810079100 A CN 201810079100A CN 108218700 A CN108218700 A CN 108218700A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/56—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
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Abstract
The invention discloses a kind of automotive upholstery specialty plasticiser TM8, plasticizer TM8 supplementary materials include：Acid anhydrides, alcohol, catalyst, sodium carbonate and filter aid；The technique for further including automotive upholstery specialty plasticiser TM8, including esterification, refined and press filtration refine, molecular distillation（Short-path distillation）, during esterification, alcohol is first added in, kettle temperature adds in trimellitic anhydride after being less than 80 DEG C, adds catalyst, when material temperature rises to 220 DEG C, starts negative reaction, as acid value≤0.1mgKOH/g, opens flash distillation, dealcoholysis；It is stripped in purification step in heating, temperature rises to 215 ± 10 DEG C of strippings, adds in filter aid diatomite and carries out refined stirring；Vacuum degree reaches within 100pa in molecular distillation step, and the inlet temperature of material is made to be maintained at 215 ± 5 DEG C, and manufacture craft raw material is easy to get, and technique sophisticated equipment is simple, and the plasticizer feature of environmental protection is good, and plasticizing efficiency is high, and high-low temperature resistant, volatility is low, smell is low, and stability is good.
Description
Technical field
The present invention relates to a kind of plasticizer, and in particular to a kind of automotive upholstery specialty plasticiser TM8.
Background technology
For domestic plasticizer mainly based on conventional plasticizers, common high temperature plasticizer can only meet the resistance to of common product
High temperature requirement, cold resistance are poor；The requirement of the high-low temperature resistants such as automotive trim instrument board plasticizer is high, and common plasticizer can not meet it
The requirements such as low fogging, low smell, high-low temperature resistant；The high plasticizer of high-low temperature resistant grade is monopolized by external plasticizer producer of state, domestic
Producer must be by high price import, with the raising that country requires VOC in automobile, the low fogging requirement of the low smell of plasticizer
It is corresponding to improve, therefore the resistance to low high temperature special purpose vehicle interior trim plasticizer of independent research becomes to substitute the development that import plasticizer is future
Gesture.
Invention content
The technical problems to be solved by the invention are that more and more automobile brands carry out production domesticization, automotive trim
Plasticizer requirement is high, needs to add high-low temperature resistant, is not precipitated when the plasticizer of low fogging, low smell is to reach a high temperature, is anti-aging,
In-car smell is low etc., the shortcomings that overcoming the prior art, provides a kind of automotive upholstery specialty plasticiser TM8, changes plasticizer raw material
It is easy to get, simple for process, plasticizer molecule amount obtained is big, and the feature of environmental protection is good, and plasticizing efficiency is high, and degree of atomization is good, high-low temperature resistant,
Volatility is low, smell is low, and stability is good.
In order to solve the above technical problems, the present invention provides a kind of automotive upholstery specialty plasticiser TM8, the plasticizer
TM8 includes following components：Acid anhydrides, alcohol, catalyst, sodium carbonate and filter aid.
The technical solution that further limits of the present invention is：
Further, in aforementioned automotive inside gadget specialty plasticiser TM8, the sum of weight of acid anhydrides and alcohol is total charged material weight, is pressed
Mass ratio meter alcohol：Acid anhydrides ＞ 2.1, catalyst account for the 0.1 ‰ -1 ‰ of total charged material weight, sodium carbonate account for total charged material weight 0.1 ‰ -
0.7 ‰, filter aid accounts for the 0.3 ‰ -1 ‰ of total charged material weight.
In aforementioned automotive inside gadget specialty plasticiser TM8, acid anhydrides is trimellitic anhydride；Alcohol is n-octyl alcohol；Catalyst is titanium
Isopropyl propionate；Filter aid is diatomite.
In aforementioned automotive inside gadget specialty plasticiser TM8, according to the mass fraction：Trimellitic anhydride：1 part, n-octyl alcohol：2.5
Part, catalyst：0.35×10-3-3.5×10-3Part, sodium carbonate：0.35×10-3-2.45×10-3Part, diatomite：1.05×10-3-3.5×10-3Part.
The present invention also designs a kind of automotive upholstery specialty plasticiser TM8, plasticizer TM8 by trimellitic anhydride, just
Octanol, isopropyl titanate, sodium carbonate, diatomite and auxiliary material are obtained through over-churning, refined, filter pressing；
Each component is as follows according to the mass fraction：According to the mass fraction：Trimellitic anhydride：1 part, n-octyl alcohol：2.5 parts, metatitanic acid isopropyl
Ester：0.35×10-3-3.5×10-3Part, sodium carbonate：0.35×10-3-2.45×10-3Part, diatomite：1.05×10-3-3.5×
10-3Part, auxiliary material：0.001-0.002 parts, wherein：
Auxiliary material is by chlorinated paraffin, levelling agent, compound rare-earth, lubricant, coupling agent, glass fiber powder, calcium/zinc stabilizer, soybean
Oil, flame-retardant system mix；
Auxiliary material each component according to the mass fraction is as follows：
Chlorinated paraffin：9-11 parts, levelling agent：8-10 parts, compound rare-earth：1-3 parts, lubricant：4-7 parts, coupling agent：8-10 parts,
Glass fiber powder：5-8 parts, calcium/zinc stabilizer：5-7 parts, soybean oil：10-13 parts, flame-retardant system：12-14 parts；
Flame-retardant system is phosphorus nitrogen silicon ternary flame retardant, retardant synergist, nano silicon dioxide, aluminium hydroxide, magnesium hydroxide, charcoal
Black, phenolic fibre, melamine cyanurate, triphenyl phosphate, diatomaceous mixture；
Lubricant is stearate, the one or several kinds in silicone master batch, silicone oil, polyethylene wax, fully refined paraffin wax, EBS；Stream
Flat agent is one kind in diacetone alcohol, acrylic acid or dimethyl silicone polymer；Coupling agent is methylvinyl organopolysiloxane；
Compound rare-earth includes following components by mass percentage：Gd：7%, Pr：18%, Sc：7%, Sm：10%；Remaining is La, more than it is each
The sum of component is 100%；Mixture of the retardant synergist for one or more of molecular sieve, expanded graphite or montmorillonite.
In aforementioned automotive inside gadget specialty plasticiser TM8, the preparation process of automotive upholstery specialty plasticiser TM8 includes
Below scheme：Esterification-refined-press filtration-molecular distillation, wherein：
（One）Esterification
It checks whether all materials system, vacuum system, heating system, cooling system and transmission system are normal, checks esterification
Whether bottom valve closes, and whether esterification tail gas emptying opens；
N-octyl alcohol is squeezed into esterifying kettle, feeding port is opened after kettle temperature is less than 80 DEG C after n-octyl alcohol has been beaten, puts into trimellitic acid
Acid anhydride covers feeding port, opens stirring；
It opens nitrogen valve on esterifying kettle and first fills 3-5 minutes N2；
Fuel tap heating is opened, esterifying kettle bottom return valve is opened when temperature rises to 150 DEG C, kettle temperature to be esterified reaches 185 DEG C
When, it opens catalyst valve and adds N on catalyst metering narrow-necked earthen jar2, catalyst is pressed into esterifying kettle；
Heat conduction fuel tap is adjusted, controls heating rate, prevents from reacting after adding in catalyst and excessively acutely causing slug, be esterified
Kettle temperature starts automatic alcohol of mending and pumps when rising to 200 DEG C；
When reaction temperature rises to 220 DEG C, tail gas blow valve is closed, negative reaction, esterification end temp control is 225 ± 10
DEG C, sampling and testing, acid value is controlled in≤0.1mgKOH/g；
After acid value≤0.1mgKOH/g qualifications, stop mending alcohol, close the valve at esterifying kettle bottom return valve and connection visor
Door opens return valve on esterifying kettle, starts to flash, slowly opens vacuum, starts dealcoholysis, takes off to when alcohol bubble is less in kettle, in kettle
When blacking up, flash distillation terminates；
（Two）Refining step
It after flash distillation, adds in alkali sodium carbonate and neutralizes, alkali number is controlled in 20 ± 10kg, neutralizes 10 ± 5 minutes time, then
Stripping, in stripping process, the later stage keeps kettle temperature in proper order steadily at 215 ± 10 DEG C, and vacuum degree control is in≤- 0.09Mpa, stripping
When observing that emersion object is less in liquid after 2.5-4h, flash-point and acid value are surveyed in sampling；
When flash-point and acid value qualification, middle control semi-finished product flash-point >=240 DEG C, acid value≤0.1mgKOH/g closes fuel tap；
It treats that kettle temperature drops to 180 ± 10 DEG C, terminates stripping, keep the temperature 30-60 minutes, in insulating process, inflated with nitrogen 3-5 times；
After heat preservation, with nitrogen vacuum breaker, tank vacuum to be pressed is opened simultaneously, when in kettle close to normal pressure, opens tank to be pressed
Bottom valve and into tank respective valves to be pressed turn material；
It opens tank cooling water to be pressed and carries out material cooling, while suck filter aid, logical nitrogen makes filter aid and material 3-5 times
It is uniformly mixed；
（Three）Press filtration
It checks whether filter is in and treats pressure condition, whether filter pump can run well, and open bottom valve to be pressed, filter pump
Valve, filter inlet valve are passed in and out, overflow valve returns pot valve to be pressed, and closes filter pump bypass valve, and filtering and discharging valve opens filter pump, into
Expect into filter；
When overflow pipe has temperature, i.e., material has been filled in filter, and half-open filter pump bypass is opened filtering and discharging valve, closed
Overflow valve is closed, circulating filtration, adjusting filter pump bypass valve makes pressure be maintained at 0.3-0.5MPa；
Observation regards material in cylinder, and during no mechanical admixture, sampling examines；
When confirming no mechanical admixture, open into semi-finished product pot valve, closing is recycled to pot valve to be pressed；
Pressure-filtering process, whether observation is normal regarding cylinder material, treats repeatedly to be blown with air compressed gas in indent, treats that press filtration material does not have
Have, gage pressure decline when, terminate press filtration；
Small finished pot sample is taken to chemically examine, molecular distillation process is transferred to after qualified；
（Four）Molecular distillation
It is intact to review and validate molecular distillation equipment use state；
The vacuum system of molecular distillation equipment is opened, runs vacuum pump so that the vacuum degree of molecular distillation equipment system does not surpass
Cross 100pa；
Heat conduction oil circulating pump is opened, the inlet temperature of material is made to be maintained at 215 ± 5 DEG C；
The bottom valve of small finished pot, the sample introduction valve of molecular distillation are opened, keeps sample introduction 20 ± 5HZ of frequency, sample introduction stream
Measure 0.6m3-1m3；
The separation speed reducer of molecular distillation equipment is opened, is kept stirring frequency as 45 ± 5HZ；
Product material is automatically separated purification weight component in molecular distillation equipment；
Heavy constituent finished product is collected, is transferred to finished pot storage.
In aforementioned automotive inside gadget specialty plasticiser TM8, the step of esterificationThere there is no esterifying kettle when adding in catalyst
Kettle pressure；From catalyst is added in the qualified sample time control of esterification acid value in 2.5-3.5h during esterification.
In aforementioned automotive inside gadget specialty plasticiser TM8, the step of esterificationWhen opening esterifying kettle bottom return valve,
Simultaneously observing tower reflux situation, when find reflux liquid level do not decline, have and directly rushed with nitrogen treatment during line clogging；Esterification is anti-
The step of answeringThe middle N2 for opening catalyst valve and adding 0.2MPa on catalyst metering narrow-necked earthen jar.
In aforementioned automotive inside gadget specialty plasticiser TM8, the step of esterificationWhen carrying out negative reaction, negative pressure value
≥-0.085Mpa。
In aforementioned automotive inside gadget specialty plasticiser TM8, refined stepIn when flash-point qualification, acid value increase when, after
Continuous to mend alkali, concrete operations are：
After closing fuel tap, continue to strip, treat that material temperature is down to 200 ± 10 DEG C, close stripping, mend alkali neutralization, mend after buck 15-20 points
Sampling detecting acid number during clock, if up to standard.
In aforementioned automotive inside gadget specialty plasticiser TM8, the concrete operations that dealcoholysis is stripped when refined are：
Water rate control is in 200-250kg/h within 0-60 minutes；Water rate control is in 250-300kg/h within 60-150 minutes；150- stripping knots
Beam water rate control is in 300-400kg/h；
Water has 10-30kg/h deviations in stripping process.
The beneficial effects of the invention are as follows：
It is the effect in order to play control heating rate that the present invention, which adjusts heat conduction fuel tap in esterification, can prevent from adding in this way
Enter to react after catalyst and excessively acutely cause slug；It is big that later stage keeps kettle temperature steadily to be avoided as possible at 215 ± 10 DEG C in proper order repeatedly
Amplitude lifts kettle temperature；
The present invention treats repeatedly to be blown with air compressed gas in indent in press filtration, can effectively prevent diatomite, activated carbon precipitation
It blocks.
The present invention adjusts heat conduction fuel tap in esterification, starts automatic alcohol of mending when being esterified kettle temperature and rising to 200 DEG C and pumps, after
Continuous alcohol of mending can carry out water and alcohol azeotropic, and band is leaked water so that react and carried out to positive reaction direction, improve reaction speed, improve
Efficiency.
Using trimellitic anhydride and n-octyl alcohol, esterification generation product boiling point is high, molecular weight is big, low fogging, low waves the present invention
Hair, low smell, high-low temperature resistant is splendid, stablizes.
Flame-retardant system is added in the plasticizer of the present invention, can effectively improve the flame retardant property of plasticizer of the present invention, when receiving
The flame-retardant systems such as rice silica, carbon black can make limit oxygen index be promoted to 6% or so, and levelling agent, compound rare-earth etc. after adding in
Addition there are synergistic effects, the flame retardant property of plasticizer of the present invention can be obviously improved, the in addition addition of flame-retardant system also carries
The mechanical property of plasticizer is risen；Soybean oil base flame-retardant plasticizer not only has good plasticising performance, while also has certain
Flame retardant property；The formula collocation of plasticizer of the present invention is reasonable, mutually coordinates, the plasticizer prepared is made to have fabulous bonding
Property and ageing resistance, service life it is long, it is not easy to rotten, flame-retardant system of the invention is mixed by multicomponent, can be made the best use of the advantages
It keeps away short, plays its maximum fire retarding effect.
Fire retardant and other fire retardant matters are mixed to form a kind of new flame-retardant system in the present invention, common flame retardant effect is big
In the sum of each flame-retardant composition independent role, synergistic effect can not only improve the efficiency of flame-retardant system, and certain in energy reduction system
The dosage of kind ingredient or whole ingredients.
Aluminium hydroxide is a kind of environment friendly flame retardant, and performance is stablized in water, light heat environment, non-volatile, and price is low
Honest and clean, raw material is easy to get, while will not discharge pernicious gas in combustion, and the residue after burning does not pollute the environment, thus
To being widely applied；Magnesium hydroxide is a kind of novel filled-type fire retardant, is discharged in burning without pernicious gas, after burning
Residue will not pollute the environment, thus increasingly extensive application has been obtained as environment friendly flame retardant.
Description of the drawings
Fig. 1 is the process flow chart of the embodiment of the present invention.
Specific embodiment
Embodiment 1
A kind of automotive upholstery specialty plasticiser TM8 provided in this embodiment, plasticizer TM8 supplementary materials include following components：
Acid anhydrides, alcohol, catalyst, sodium carbonate and filter aid.
In the present embodiment, the sum of weight of acid anhydrides and alcohol is total charged material weight, counts alcohol in mass ratio：Acid anhydrides ＞ 2.1, is urged
Agent accounts for the 0.1 ‰ -1 ‰ of total charged material weight, and sodium carbonate accounts for the 0.1 ‰ -0.7 ‰ of total charged material weight, and filter aid accounts for the weight that always feeds intake
The 0.3 ‰ -1 ‰ of amount；
Acid anhydrides is trimellitic anhydride；Alcohol is n-octyl alcohol；Catalyst is isopropyl titanate；Filter aid is diatomite.
The preparation process of automotive upholstery specialty plasticiser TM8 is as follows：
1. trimellitic anhydride and n-octyl alcohol input esterifying kettle esterification, after acid value qualification to be esterified；
2. being transferred to refining step, refining step includes the trimellitic acid monoesters that alkali neutralization is added not complete reaction；It is total to using water alcohol
Excessive n-octyl alcohol is isolated in boiling, and heat preservation removes moisture in material；
3. it is transferred to press filtration process：The mechanical admixture in material is filtered out, makes material clear without miscellaneous；
4. it is transferred to molecular distillation process：By distillation process, the low-boiling-point substance in material is made to evaporate removing, improves the degree of atomization of material
With reduction volatile quantity, VOC smells are reduced.
Molecular distillation technological principle：Material is passed through in molecular distillation equipment, the scraper plate in molecular distillation equipment is material
Film-form is spread to, increases disengagement area, makes the low-boiling-point substance rapid evaporation in by-product, the purity of product is improved, so as to improve mist
Change degree and reduction volatility, mitigate VOC smells.
Embodiment 2
Specific automotive upholstery specialty plasticiser TM8, plasticizer TM8 supplementary materials are pressed in embodiment 1 provided in this embodiment
Mass fraction meter includes：Trimellitic anhydride：1 part, n-octyl alcohol：2.5 parts, catalyst：0.35×10-3-3.5×10-3Part, carbonic acid
Sodium：0.35×10-3-2.45×10-3Part, diatomite：1.05×10-3-3.5×10-3Part.
The preparation process of above-mentioned automotive upholstery specialty plasticiser TM8 is as shown in Figure 1, including below scheme：Esterification-essence
System-press filtration-molecular distillation, wherein：
（One）Esterification
It checks whether all materials system, vacuum system, heating system, cooling system and transmission system are normal, checks esterification
Whether bottom valve closes, and whether esterification tail gas emptying opens；
N-octyl alcohol is squeezed into esterifying kettle, feeding port is opened after kettle temperature is less than 80 DEG C after n-octyl alcohol has been beaten, puts into trimellitic acid
Acid anhydride covers feeding port, opens stirring；
It opens nitrogen valve on esterifying kettle and first fills 3-5 minutes N2；
Fuel tap heating is opened, esterifying kettle bottom return valve is opened when temperature rises to 150 DEG C, kettle temperature to be esterified reaches 185 DEG C
When, it opens catalyst valve and adds 0.2MPaN on catalyst metering narrow-necked earthen jar2, 5kg catalyst is pressed into esterifying kettle；
Heat conduction fuel tap is adjusted, controls heating rate, prevents from reacting after adding in catalyst and excessively acutely causing slug, be esterified
Kettle temperature starts the automatic speed mended alcohol pump, benefit alcohol is controlled according to the size of regurgitant volume when rising to 200 DEG C；
When reaction temperature rises to 220 DEG C, tail gas blow valve, negative reaction, according to response situation in kettle and regurgitant volume are closed
Size control vacuum degree size, negative pressure value >=-0.085Mpa, at 225 ± 10 DEG C, sampling is surveyed for esterification end temp control
Examination, acid value are controlled in≤0.1mgKOH/g；
After acid value≤0.1mgKOH/g qualifications, stop mending alcohol, close the valve at esterifying kettle bottom return valve and connection visor
Door opens return valve on esterifying kettle, starts to flash, and slowly opens vacuum, vacuum size, depending on material boiling and regurgitant volume situation in kettle
Depending on, start dealcoholysis, take off to when alcohol bubble is less in kettle, when blacking up in kettle, flash distillation terminates；
（Two）Refining step
It after flash distillation, adds in alkali sodium carbonate and neutralizes, alkali number is controlled in 20 ± 10kg, neutralizes 10 ± 5 minutes time, then
Stripping, in stripping process, the later stage keeps kettle temperature to avoid significantly lifting kettle temperature repeatedly as possible in proper order steadily at 215 ± 10 DEG C,
Vacuum degree control is stripped when observing that emersion object is less in liquid after 2.5-4h, flash-point and acid value are surveyed in sampling in≤- 0.09Mpa；
When flash-point and acid value qualification, middle control semi-finished product flash-point >=240 DEG C, acid value≤0.1mgKOH/g closes fuel tap；
It treats that kettle temperature drops to 180 ± 10 DEG C, terminates stripping, keep the temperature 30-60 minutes, in insulating process, inflated with nitrogen 3-5 times；
After heat preservation, with nitrogen vacuum breaker, tank vacuum to be pressed is opened simultaneously, when in kettle close to normal pressure, opens tank to be pressed
Bottom valve and into tank respective valves to be pressed turn material；
It opens tank cooling water to be pressed and carries out material cooling, while suck filter aid, logical nitrogen makes filter aid and material 3-5 times
It is uniformly mixed；
（Three）Press filtration
It checks whether filter is in and treats pressure condition, whether filter pump can run well, and open bottom valve to be pressed, filter pump
Valve, filter inlet valve are passed in and out, overflow valve returns pot valve to be pressed, and closes filter pump bypass valve, and filtering and discharging valve opens filter pump, into
Expect that hermetic filtering machine and flame filter press operation are different into filter, pay attention to distinguishing；
When overflow pipe has temperature, i.e., material has been filled in filter, and half-open filter pump bypass is opened filtering and discharging valve, closed
Overflow valve is closed, circulating filtration, adjusting filter pump bypass valve makes pressure be maintained at 0.3-0.5MPa；
Observation regards material in cylinder, and during no mechanical admixture, sampling examines；
When confirming no mechanical admixture, open into semi-finished product pot valve, closing is recycled to pot valve to be pressed；
Pressure-filtering process, whether observation is normal regarding cylinder material, treats repeatedly to be blown with air compressed gas in indent, treats that press filtration material does not have
Have, gage pressure decline when, terminate press filtration；
Small finished pot sample is taken to chemically examine, molecular distillation process is transferred to after qualified；
（Four）Molecular distillation
It is intact to review and validate molecular distillation equipment use state；
The vacuum system of molecular distillation equipment is opened, runs vacuum pump so that the vacuum degree of molecular distillation equipment system does not surpass
Cross 100pa；
Heat conduction oil circulating pump is opened, the inlet temperature of material is made to be maintained at 215 ± 5 DEG C；
The bottom valve of small finished pot, the sample introduction valve of molecular distillation are opened, keeps sample introduction 20 ± 5HZ of frequency, sample introduction stream
Measure 0.6m3-1m3；
The separation speed reducer of molecular distillation equipment is opened, is kept stirring frequency as 45 ± 5HZ；
Product material is automatically separated purification weight component in molecular distillation equipment；
Heavy constituent finished product is collected, is transferred to finished pot storage.
In the present embodiment, the step of esterificationEsterifying kettle does not have kettle pressure when adding in catalyst；During esterification from
Catalyst is added in the qualified sample time control of esterification acid value in 2.5-3.5h.
In the present embodiment, the step of esterificationWhen opening esterifying kettle bottom return valve, while observing tower reflux feelings
Condition, when find reflux liquid level do not decline, have and directly rushed with nitrogen treatment during line clogging.
In the present embodiment, refined stepIn when flash-point qualification, when acid value increases, continue to mend alkali, concrete operations are：
After closing fuel tap, continue to strip, treat that material temperature is down to 200 ± 10 DEG C, close stripping, mend alkali neutralization, mend after buck 15-20 points
Sampling detecting acid number during clock, if up to standard.
In the present embodiment, refine when stripping dealcoholysis concrete operations be：
Water rate control is in 200-250kg/h within 0-60 minutes；Water rate control is in 250-300kg/h within 60-150 minutes；150- stripping knots
Beam water rate control is in 300-400kg/h；
Water has 10-30kg/h deviations in stripping process.
In the present embodiment, as temperature height cause alcohol proportion reduce or esterification acid value decline in esterification time it is slow when,
Can suitably it add into 200-400kg fresh alcohols.
The physicochemical property determination data of plasticizer TM8, is specifically shown in Table 1 in the embodiment of the present invention；
The physicochemical property determination data of 1 plasticizer TM8 of table
| Inspection project | Inspection result | The method of inspection |
| Appearance | It is transparent without miscellaneous | Range estimation |
| Coloration,（Platinum-cobalt）Number | 45 | GB/T 1664 |
| Acid value, mgKOH/g | 0.019 | GB/T 1668 |
| Proportion, (20/20 DEG C) | 0.980 | GB/T 4472 |
| Ester content wt% | 99.8 | GC |
| Moisture wt% | 0.029 | GB/T 6283 |
| Flash-point (opening agar diffusion method）℃ | 247 | GB/T 1671 |
| Viscosity（20℃）mpa·s | 125 | GB/T 2794 |
| Heating loss wt ﹪ | 0.018 | GB/T 1669 |
| Free alcohol content Ppm w/w | 50 | GC |
| Degree of atomization mg | 0.15 | DIN75201-B |
Physicochemical property by the visible plasticizer T8M of the present invention of table 1 is excellent, have boiling point is high, big, low fogging, the low volatilization of molecular weight,
High-low temperature resistant is splendid, stablizes.
The degree of atomization of the plasticizer of the present invention and conventional several plasticizer are compared using DIN75201/B methods, had
Body is shown in Table 2；
The atomization degrees of data of the plasticizer and conventional several plasticizer of 2 present invention of table
| Plasticizer type | DOP | DPHP | DIDP | TOTM | Plasticizer of the present invention |
| Degree of atomization（mg） | 4.9 | 1.0 | 0.8 | 0.3 | 0.15 |
There is relatively low degree of atomization, raising property itself compared to traditional plasticizer by the plasticizer TM8 of the 2 visible present invention of table
Can, it is made to meet stronger use environment.
The plasdcizing rate of plasticizer TM8 of the present invention with common plasticizer is compared, is specifically shown in Table 3：
The plasdcizing rate correction data of plasticizer and common plasticizer of the present invention
| Abbreviation | Chemical name | Molecular weight | Substitution index |
| DOP | Diisooctyl phthalate | 390 | 0.97 |
| TOTM | Three different monooctyl ester of trimellitic anhydride | 546 | 1.17 |
| TM810 | Tri trimellitate（Just pungent, the positive last of the ten Heavenly stems）Ester | 592 | 1.12 |
| TM8 of the present invention | Tri trimellitate n-octyl | 546 | 1.10 |
In table 3, substitution index=at room temperature, reach shore hardness（A）The plasticizer number of 80 requirements（PHR）With DOP dosages
（52.9 parts）Ratio.
By table 3 as it can be seen that plasticizer TM8 plasdcizing rates of the present invention compared to by for plasticizer have good plasdcizing rate,
Feeling is better for product.
The manufacture craft of the plasticizer of the present invention, raw materials technology are easy to get, and technique sophisticated equipment is simple, plasticizer ring obtained
Guarantor property is good, and plasticizing efficiency is high, and high-low temperature resistant, volatility is low, and stability is good.
Embodiment 3
The present embodiment also provides a kind of automotive upholstery specialty plasticiser TM8, plasticizer TM8 by trimellitic anhydride, it is just pungent
Alcohol, isopropyl titanate, sodium carbonate, diatomite and auxiliary material are obtained through over-churning, refined, filter pressing；
Each component is as follows according to the mass fraction：According to the mass fraction：Trimellitic anhydride：1 part, n-octyl alcohol：2.5 parts, metatitanic acid isopropyl
Ester：0.35×10-3-3.5×10-3Part, sodium carbonate：0.35×10-3-2.45×10-3Part, diatomite：1.05×10-3-3.5×
10-3Part, auxiliary material：0.001-0.002 parts, wherein：
Auxiliary material is by chlorinated paraffin, levelling agent, compound rare-earth, lubricant, coupling agent, glass fiber powder, calcium/zinc stabilizer, soybean
Oil, flame-retardant system mix；
Auxiliary material each component according to the mass fraction is as follows：
Chlorinated paraffin：9-11 parts, levelling agent：8-10 parts, compound rare-earth：1-3 parts, lubricant：4-7 parts, coupling agent：8-10 parts,
Glass fiber powder：5-8 parts, calcium/zinc stabilizer：5-7 parts, soybean oil：10-13 parts, flame-retardant system：12-14 parts；
Flame-retardant system is phosphorus nitrogen silicon ternary flame retardant, retardant synergist, nano silicon dioxide, aluminium hydroxide, magnesium hydroxide, charcoal
It is black, phenolic fibre, melamine cyanurate, triphenyl phosphate, diatomaceous mixture；
Lubricant is stearate, the one or several kinds in silicone master batch, silicone oil, polyethylene wax, fully refined paraffin wax, EBS；Stream
Flat agent is one kind in diacetone alcohol, acrylic acid or dimethyl silicone polymer；Coupling agent is methylvinyl organopolysiloxane；
Compound rare-earth includes following components by mass percentage：Gd：7%, Pr：18%, Sc：7%, Sm：10%；Remaining is La, more than it is each
The sum of component is 100%；Mixture of the retardant synergist for one or more of molecular sieve, expanded graphite or montmorillonite.
In the present embodiment, phosphorus nitrogen silicon ternary flame retardant prepare it is specific as follows：
（1）Nitrogen 5-10min is passed through into the three-necked flask equipped with condenser pipe, dropping funel, sequentially adds phosphoric acid and ethyl alcohol, it will
γ-（2,3- glycidoxies）Propyl front three oxosilane is added dropwise, and rate of addition is controlled in 3-5g/min, is reacted at room temperature
3-4h；After reaction, three-necked flask is placed in thermostat water bath, is evaporated under reduced pressure with rotary evaporator and removes solvent and low boiling
Object is to get to phosphorus silicon binary fire retardant.Wherein entire reaction process keeps continuous mechanical agitation, mixing speed 300-400r/
min；
（2）Phosphorus silicon binary fire retardant and urea are added in a reservoir, and continuous mechanical agitation 5-10min, obtains phosphorus nitrogen silicon three at room temperature
First fire retardant.
The volume ratio of phosphoric acid and ethyl alcohol is 1:3, phosphoric acid and γ-（2,3- glycidoxies）Mole of propyl front three oxosilane
Than being 1:1；The mass ratio of phosphorus silicon binary fire retardant and urea is 1:3.
The present invention is still prepared in the preparation according to the preparation method for implementing the plasticizer in 1-2, is finally added in before press filtration
Auxiliary material is uniformly mixed preparation.
The plasticizer principal component obtained in embodiment：Tri trimellitate n-octyl content >=99%.
In addition to the implementation, the present invention can also have other embodiment.It is all to use equivalent substitution or equivalent transformation shape
Into technical solution, all fall within the present invention claims protection domain.
Claims (10)
1. a kind of automotive upholstery specialty plasticiser TM8, it is characterised in that：Plasticizer TM8 passes through alcohol and acid anhydrides and catalyst
Esterification, then sodium carbonate is added to refine, finally plus filter aid press filtration is made.
2. automotive upholstery specialty plasticiser TM8 according to claim 1, it is characterised in that：The weight of the acid anhydrides and alcohol
The sum of amount is total charged material weight, described to count alcohol in mass ratio：Acid anhydrides ＞ 2.1, the catalyst account for total charged material weight 0.1 ‰-
1 ‰, the sodium carbonate accounts for the 0.1 ‰ -0.7 ‰ of total charged material weight, and filter aid accounts for the 0.3 ‰ -1 ‰ of total charged material weight.
3. automotive upholstery specialty plasticiser TM8 according to claim 2, it is characterised in that：The acid anhydrides is inclined benzene
Three acid anhydrides；The alcohol is n-octyl alcohol；The catalyst is isopropyl titanate；The filter aid is diatomite.
4. automotive upholstery specialty plasticiser TM8 according to claim 3, it is characterised in that：According to the mass fraction：Inclined benzene
Three acid anhydrides：1 part, n-octyl alcohol：2.5 parts, catalyst：0.35×10-3-3.5×10-3Part, sodium carbonate：0.35×10-3-2.45×
10-3Part, diatomite：1.05×10-3-3.5×10-3Part.
5. a kind of automotive upholstery specialty plasticiser TM8, it is characterised in that：Plasticizer TM8 by trimellitic anhydride, it is just pungent
Alcohol, isopropyl titanate, sodium carbonate, diatomite and auxiliary material are obtained through over-churning, refined, filter pressing；
Each component is as follows according to the mass fraction：According to the mass fraction：Trimellitic anhydride：1 part, n-octyl alcohol：2.5 parts, metatitanic acid isopropyl
Ester：0.35×10-3-3.5×10-3Part, sodium carbonate：0.35×10-3-2.45×10-3Part, diatomite：1.05×10-3-3.5×
10-3Part, auxiliary material：0.001-0.002 parts, wherein：
The auxiliary material is stablized by chlorinated paraffin, levelling agent, compound rare-earth, lubricant, coupling agent, glass fiber powder, calcium/zinc
Agent, soybean oil, flame-retardant system mix；
Auxiliary material each component according to the mass fraction is as follows：
Chlorinated paraffin：9-11 parts, levelling agent：8-10 parts, compound rare-earth：1-3 parts, lubricant：4-7 parts, coupling agent：8-10 parts,
Glass fiber powder：5-8 parts, calcium/zinc stabilizer：5-7 parts, soybean oil：10-13 parts, flame-retardant system：12-14 parts；
The flame-retardant system is phosphorus nitrogen silicon ternary flame retardant, retardant synergist, nano silicon dioxide, aluminium hydroxide, hydroxide
Magnesium, carbon black, phenolic fibre, melamine cyanurate, triphenyl phosphate, diatomaceous mixture；
The lubricant is stearate, a kind of or several in silicone master batch, silicone oil, polyethylene wax, fully refined paraffin wax, EBS
Kind；The levelling agent is one kind in diacetone alcohol, acrylic acid or dimethyl silicone polymer；The coupling agent is methyl second
Alkenyl organopolysiloxane；The compound rare-earth includes following components by mass percentage：Gd：7%, Pr：18%, Sc：7%,
Sm：10%；Remaining is that the sum of La, the above components is 100%；The retardant synergist is molecular sieve, expanded graphite or montmorillonite
One or more of mixture.
6. automotive upholstery specialty plasticiser TM8 according to claim 4, it is characterised in that：The automotive upholstery is special
The preparation process of plasticizer TM8 includes below scheme：Esterification-refined-press filtration-molecular distillation, wherein：
（One）Esterification
It checks whether all materials system, vacuum system, heating system, cooling system and transmission system are normal, checks esterification
Whether bottom valve closes, and whether esterification tail gas emptying opens；
N-octyl alcohol is squeezed into esterifying kettle, feeding port is opened after kettle temperature is less than 80 DEG C after n-octyl alcohol has been beaten, puts into trimellitic acid
Acid anhydride covers feeding port, opens stirring；
It opens nitrogen valve on esterifying kettle and first fills 3-5 minutes N2；
Fuel tap heating is opened, esterifying kettle bottom return valve is opened when temperature rises to 150 DEG C, when kettle temperature to be esterified reaches 185 DEG C,
It opens catalyst valve and adds N on catalyst metering narrow-necked earthen jar2, catalyst is pressed into esterifying kettle；
Heat conduction fuel tap is adjusted, starts automatic benefit alcohol pump when being esterified kettle temperature and rising to 200 DEG C；
When reaction temperature rises to 220 DEG C, tail gas blow valve is closed, negative reaction, esterification end temp control is 225 ± 10
DEG C, sampling and testing, acid value is controlled in≤0.1mgKOH/g；
After acid value≤0.1mgKOH/g qualifications, stop mending alcohol, close the valve at esterifying kettle bottom return valve and connection visor,
Return valve on esterifying kettle is opened, starts to flash, slowly opens vacuum, starts dealcoholysis, is taken off to when alcohol bubble is less in kettle, it is blacking up in kettle
When, flash distillation terminates；
（Two）Refining step
It after flash distillation, adds in alkali sodium carbonate and neutralizes, alkali number is controlled in 20 ± 10kg, neutralizes 10 ± 5 minutes time, then vapour
It carries, in stripping process, the later stage keeps kettle temperature in proper order steadily at 215 ± 5 DEG C, and vacuum degree control is in≤- 0.09Mpa, stripping
When 2.5-4h observes that emersion object is less in liquid, flash-point and acid value are surveyed in sampling；
When flash-point and acid value qualification, middle control semi-finished product flash-point >=240 DEG C, acid value≤0.1mgKOH/g closes fuel tap；
It treats that kettle temperature drops to 180 ± 10 DEG C, terminates stripping, keep the temperature 30-60 minutes, in insulating process, inflated with nitrogen 3-5 times；
After heat preservation, with nitrogen vacuum breaker, tank vacuum to be pressed is opened simultaneously, when in kettle close to normal pressure, opens tank to be pressed
Bottom valve and into tank respective valves to be pressed turn material；
It opens tank cooling water to be pressed and carries out material cooling, while suck filter aid, logical nitrogen mixes filter aid and material 3-5 times
It closes uniform；
（Three）Press filtration
Check whether filter is in and treats pressure condition, whether filter pump can run well, and open bottom valve to be pressed, filter pump into
Go out valve, filter inlet valve, overflow valve returns pot valve to be pressed, and closes filter pump bypass valve, and filtering and discharging valve opens filter pump, feeds
Enter filter；
When overflow pipe has temperature, i.e., material has been filled in filter, and half-open filter pump bypass is opened filtering and discharging valve, closed
Overflow valve is closed, circulating filtration, adjusting filter pump bypass valve makes pressure be maintained at 0.3-0.5MPa；
Observation regards material in cylinder, and during no mechanical admixture, sampling examines；
When confirming no mechanical admixture, open into semi-finished product pot valve, closing is recycled to pot valve to be pressed；
Pressure-filtering process, whether observation is normal regarding cylinder material, treats repeatedly to be blown with air compressed gas in indent, treats that press filtration material does not have
Have, gage pressure decline when, terminate press filtration；
Small finished pot sample is taken to chemically examine, molecular distillation process is transferred to after qualified；
（Four）Molecular distillation
It is intact to review and validate molecular distillation equipment use state；
The vacuum system of molecular distillation equipment is opened, runs vacuum pump so that the vacuum degree of molecular distillation equipment system does not surpass
Cross 100pa；
Heat conduction oil circulating pump is opened, the inlet temperature of material is made to be maintained at 215 ± 5 DEG C；
The bottom valve of small finished pot, the sample introduction valve of molecular distillation are opened, keeps sample introduction 20 ± 5HZ of frequency, sample introduction flow
0.6m3-1m3；
The separation speed reducer of molecular distillation equipment is opened, is kept stirring frequency as 45 ± 5HZ；
Product material is automatically separated purification weight component in molecular distillation equipment；
Heavy constituent finished product is collected, is transferred to finished pot storage.
7. automotive upholstery specialty plasticiser TM8 according to claim 6, it is characterised in that：The step of esterification
Esterifying kettle does not have kettle pressure when adding in catalyst；Exist during esterification from addition catalyst to the qualified sample time control of esterification acid value
2.5-3.5h。
8. automotive upholstery specialty plasticiser TM8 according to claim 6, it is characterised in that：The step of esterification
When opening esterifying kettle bottom return valve, at the same observing tower reflux situation, when find reflux liquid level do not decline, when having line clogging
It is directly rushed with nitrogen treatment；The step of esterificationThe middle N for opening catalyst valve and adding 0.2MPa on catalyst metering narrow-necked earthen jar2；
The step of esterificationWhen carrying out negative reaction, negative pressure value >=-0.085Mpa.
9. automotive upholstery specialty plasticiser TM8 according to claim 6, it is characterised in that：Refined stepIn when
Flash-point is qualified, when acid value increases, continues to mend alkali, concrete operations are：
After closing fuel tap, continue to strip, treat that material temperature is down to 200 ± 10 DEG C, close stripping, mend alkali neutralization, mend after buck 15-20 points
Sampling detecting acid number during clock, if up to standard.
10. automotive upholstery specialty plasticiser TM8 according to claim 6, it is characterised in that：Stripping dealcoholysis when refined
Concrete operations are：
Water rate control is in 200-250kg/h within 0-60 minutes；Water rate control is in 250-300kg/h within 60-150 minutes；150- stripping knots
Beam water rate control is in 300-400kg/h；
Water has 10-30kg/h deviations in stripping process.
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| CN201810079100.6A CN108218700A (en) | 2018-01-26 | 2018-01-26 | A kind of automotive upholstery specialty plasticiser TM8 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109503371A (en) * | 2018-12-17 | 2019-03-22 | 江苏森禾化工科技有限公司 | A kind of preparation method of low VOC environment-friendlyweather-proof weather-proof plasticizer |
| CN114805928A (en) * | 2022-03-10 | 2022-07-29 | 江苏森禾化工科技有限公司 | Metabenzene bio-based plasticizer |
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