CN106589466A - Environment-friendly low-temperature-resistant fire-retardant complex plasticizer - Google Patents
Environment-friendly low-temperature-resistant fire-retardant complex plasticizer Download PDFInfo
- Publication number
- CN106589466A CN106589466A CN201611066284.XA CN201611066284A CN106589466A CN 106589466 A CN106589466 A CN 106589466A CN 201611066284 A CN201611066284 A CN 201611066284A CN 106589466 A CN106589466 A CN 106589466A
- Authority
- CN
- China
- Prior art keywords
- parts
- decanol
- decanedioic acid
- low temperature
- flame retardant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
-
- 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
-
- 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
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/16—Halogen-containing compounds
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- 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
- C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids
-
- 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
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5425—Silicon-containing compounds containing oxygen containing at least one C=C bond
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/322—Ammonium phosphate
- C08K2003/323—Ammonium polyphosphate
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/04—Antistatic
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention discloses an environment-friendly low-temperature-resistant fire-retardant complex plasticizer, comprising a matrix of the plasticizer, the matrix is prepared from sebacic acid, decyl alcohol, a catalyst, sodium carbonate and an auxiliary by exetrification, refining, filter-press refining and distilling. The weight ratio of sebacic acid to decyl alcohol is 1 to 1.57-5. The adding amount of the catalyst is 0.2-1% of the total weight of sebacic acid and decyl alcohol, the adding amount of sodium carbonate is 0.1-0.7% of the total weight of sebacic acid and decyl alcohol and the adding amount of the auxiliary is 0.3-1% of the total weight of sebacic acid and decyl alcohol. The plasticizer also comprises a low-temperature-resistant fire-retardant system. The plasticizer disclosed by the invention has the advantages of great environmental friendliness, high plasticizing efficiency, low-temperature resistance, low volatility, extremely low volatility and great stability.
Description
Technical field
The present invention relates to a kind of plasticizer, specifically a kind of environmentally friendly low temperature resistant flame retardant composite elasticizer.
Background technology
Plasticizer is a kind of macromolecular material auxiliary agent, and its species is various, and modal kind is DEHP（Trade name
DOP）, DEHP chemical names phthalic acid two (2- ethyl hexyls) ester is a kind of colourless, liquid with no taste, is industrially widely used.Increase
Modeling agent is the macromolecular material auxiliary agent being industrially widely used, and this material is added in plastic processing, and its can be made flexible
Property strengthen, be easily worked, can be legal for industrial use.Existing common low temperature resistant plasticizer is easily waved because of the little low boiling point of molecular weight
Send out, life-time service post-plasticization agent is separated out from product, so as to directly affect the lower temperature resistance of its product, affect the life-span of product,
Easily harden, ftracture, tolerance to cold is deteriorated, product cracking, the problems such as fold, service life greatly reduces.
The content of the invention
The technical problem to be solved is：
(1) how the low temperature resistant flame retardant performance of plasticizer product of the present invention is improved by adding low temperature resistant flame retardant system；
(2) the low technology of plasticizer Mechanical Properties of Products of the present invention is caused after how improving due to adding low temperature resistant flame retardant system
Problem.
The present invention solves the technical scheme of above technical problem：
A kind of environmentally friendly low temperature resistant flame retardant composite elasticizer, including plasticizer matrix, plasticizer matrix is by decanedioic acid, decanol, catalysis
Agent, sodium carbonate and adjuvant are through being esterified, refined, filter pressing is refined, distillation is obtained；The weight of decanedioic acid and decanol is：The last of the ten Heavenly stems
Diacid：1 part, decanol：1.57-5 part；The addition of catalyst is the 0.2-1% of decanedioic acid and decanol gross weight, sodium carbonate plus
Enter the 0.1-0.7% that amount is decanedioic acid and decanol gross weight, the addition of adjuvant is the 0.3-1% of decanedioic acid and decanol gross weight；
Also include low temperature resistant flame retardant system, the addition of low temperature resistant flame retardant system is the 1.7-1.9% of plasticizer matrix weight；Fire retardant
The component of the weight portion of system is configured to：Nano silicon：8.7-8.9 part, fume colloidal silica：3.5-3.7 part, methyl hydrogen
Silicone oil：71-73 parts, hydroxyl polydimethylsiloxane：9.7-9.9 part, vinyltrimethoxy silane：3-5 parts, APP：
6.5-6.7 part, reactive diluent：1.5-1.7 part, compatilizer：1.2-1.3 part, coupling agent：0.5-0.7 parts, levelling agent：1.2-
1.4 part, mixed chlorinated rare earth：0.1-0.3 parts；The particle diameter of described nano silicon is 20-30nm.
The technical scheme that further limits of the invention is：
Aforesaid environmentally friendly low temperature resistant flame retardant composite elasticizer, catalyst is isopropyl titanate, tetrabutyl titanate and p-methyl benzenesulfonic acid
In one or more mixing；Adjuvant is kieselguhr or activated carbon.
Aforesaid environmentally friendly low temperature resistant flame retardant composite elasticizer, reactive diluent is alkyl glycidyl ether, the acid shrink of pungent certain herbaceous plants with big flowers
One kind or one in glyceride, trihydroxymethylpropanyltri diglycidyl ether, toluene glycidyl ether, Oleum Ricini polyglycidyl ether
Plant thing mixed above；Compatilizer is maleic anhydride grafted PP；Coupling agent is vinyl tributyl ketoximyl silane coupling
One or more mixture in agent, methylvinyldichlorosilane coupling agent, methyl tributanoximo silane coupling agent；
Levelling agent is isophorone, DAA, fluorin modified crylic acid, phosphate modified acrylic acid, acrylic acid, polydimethylsiloxanes
One or more mixture in alkane, poly- methyl alkyl siloxane, organic modified polyorganosiloxane.
Aforesaid environmentally friendly low temperature resistant flame retardant composite elasticizer, plasticizer matrix is obtained according to the following steps：
(i) it is esterified：The decanol for measuring is squeezed into into reactor by proportioning, temperature of reaction kettle adds the last of the ten Heavenly stems two after being less than 80 DEG C by proportioning
Acid, then, when material temperature rises to 220-225 DEG C, starts negative reaction, as acid number ＜ by proportioning addition catalyst again
0.1mgKOH/g, carries out flash distillation dealcoholysis；
(ii) refine：Flash distillation adds sodium carbonate to be neutralized after terminating by proportioning, neutralizes minute time 10-30, temperature of reaction kettle liter
During to 200-210 DEG C, start stripping, then material temperature keeps 200-210 DEG C of stripping 2.5-3h, and cools down after being incubated half an hour, and
Adjuvant is added to carry out refined stirring by proportioning；
(iii) filter pressing is refined：Adjust filter pump bypass valve make the intrinsic pressure power of filter be maintained at 0.3～0.5Mpa, treat filter pressing material without and
In filter during pressure drop, terminate filter pressing；
(iv) distill：The vacuum system of molecular distillation equipment is opened, vacuum pump is run so that the vacuum of molecular distillation equipment system
Within reaching 100pa, heat conduction oil circulating pump is opened, the material inlet temperature for making molecular distillation equipment system is maintained at 175-185
DEG C, the bottom valve of finished pot and the sample introduction valve of molecular distillation equipment system are opened, sample introduction 35 ± 5HZ of frequency is kept, enter
Sample flow 0.7m3-1.2m3, the separation reductor of molecular distillation equipment is opened, it is 45 ± 5HZ to be kept stirring for frequency, and product is dividing
Purification weight component is automatically separated in sub- distillation equipment, heavy constituent finished product is collected, finished pot storage is proceeded to.
The processing technology of the plasticizer matrix of the present invention, raw materials technology is easy to get, and technique sophisticated equipment is simple, obtained plasticising
The agent matrix feature of environmental protection is good, and plasticizing efficiency is high, and low temperature resistant, volatility is low, volatility is extremely low, good stability.The plasticizer of the present invention
Matrix contrasts as follows with the degree of atomization of existing plasticizer：DOP：4.9mg, DOA：5.5mg, DINA：2.5mg, DOS：1.2mg, this
Invention plasticizer matrix：0.3mg.
The invention has the beneficial effects as follows：Experimental result shows that the low temperature resistant flame retardant system of the present invention can be effectively improved this
The fire resistance and resistance to low temperature of bright plasticizer plastic, when nano silicon, fume colloidal silica, methyl hydrogen
Silicone oil, hydroxyl polydimethylsiloxane, vinyltrimethoxy silane and APP composition low temperature resistant flame retardant system is added and increased
After modeling agent matrix weight, limited oxygen index can be made to be promoted to 5% or so, and reactive diluent, compatilizer, coupling agent, levelling agent and
There is synergistic effect in the addition of mixed chlorinated rare earth, can be obviously improved the fire resistance of plasticizer plastic of the present invention, make pole
Limited oxygen index further lifts 9% or so, can resist cold to subzero 20 DEG C or so；Found by SEM observations, nano silicon,
Fume colloidal silica, Methyl Hydrogen Polysiloxane Fluid, hydroxyl polydimethylsiloxane, vinyltrimethoxy silane and APP composition
Low temperature resistant flame retardant system dispersibility in plasticizer matrix is poor, add reactive diluent, compatilizer, coupling agent, levelling agent and
The dispersibility of low temperature resistant flame retardant system can be improved after mixed chlorinated rare earth；In addition, the addition of low temperature resistant flame retardant system can make this
The mechanical property of invention plasticizer plastic is compared existing product and has been declined, but with the addition of reactive diluent, compatilizer, idol
After connection agent, levelling agent and mixed chlorinated rare earth their mechanical property can be made to make moderate progress.Synthesis result shows, low temperature resistant flame retardant
The addition of system is the 1.7-1.9% of plasticizer matrix weight, and plasticizer plastic flame retarding efficiency of the present invention is high, and burns
When smoke it is little, environmental friendliness, its fire resistance, three kinds of performances of mechanical property and resistance to low temperature reach an equilibrium point, resistance
Combustion performance, mechanical property and resistance to low temperature are more excellent.In addition, the addition of low temperature resistant flame retardant system of the present invention can also be carried effectively
The antistatic performance of high plasticizer plastic of the present invention, obtains unexpected technique effect.In sum, the present invention is logical
Cross addition low temperature resistant flame retardant system, can improve the fire resistance of plasticizer plastic, mechanical property, resistance to low temperature and
Antistatic property.By plasticizer matrix obtained in the technique of the present invention, good with the feature of environmental protection, plasticizing efficiency is high, low temperature resistant, waves
The low, volatility of the property sent out is extremely low, good stability advantage.
Specific embodiment
Embodiment 1
The present embodiment is a kind of environmentally friendly low temperature resistant flame retardant composite elasticizer, including plasticizer matrix, plasticizer matrix by decanedioic acid,
Decanol, catalyst, sodium carbonate and adjuvant are through being esterified, refined, filter pressing is refined, distillation is obtained；The weight portion of decanedioic acid and decanol
Proportioning is：Decanedioic acid：1 part, decanol：1.57 part；The addition of catalyst is the 0.2% of decanedioic acid and decanol gross weight, sodium carbonate
Addition be the 0.1% of decanedioic acid and decanol gross weight, the addition of adjuvant is the 0.3% of decanedioic acid and decanol gross weight；Also
Including low temperature resistant flame retardant system, the addition of low temperature resistant flame retardant system is the 1.7% of plasticizer matrix weight；The weight of flame-retardant system
The component of amount part is configured to：Nano silicon：8.7 parts, fume colloidal silica：3.5 parts, Methyl Hydrogen Polysiloxane Fluid：71 parts, hydroxyl
Polydimethylsiloxane：9.7 parts, vinyltrimethoxy silane：3 parts, APP：6.5 parts, reactive diluent：1.5 parts,
Compatilizer：1.2 parts, coupling agent：0.5 part, levelling agent：1.2 parts, mixed chlorinated rare earth：0.1 part；Described nano silicon
Particle diameter be 20nm.
Wherein, catalyst is one or more mixing in isopropyl titanate, tetrabutyl titanate and p-methyl benzenesulfonic acid；Adjuvant
For kieselguhr or activated carbon；Reactive diluent is alkyl glycidyl ether, pungent certain herbaceous plants with big flowers acid glycidyl ester, trimethylolpropane tris
One or more mixture in glycidyl ether, toluene glycidyl ether, Oleum Ricini polyglycidyl ether；Compatilizer is
Maleic anhydride grafted PP；Coupling agent is vinyl tributyl ketoximyl silane coupling agent, methylvinyldichlorosilane
One or more mixture in coupling agent, methyl tributanoximo silane coupling agent；Levelling agent is isophorone, dipropyl
Keto-alcohol, fluorin modified crylic acid, phosphate modified acrylic acid, acrylic acid, polydimethylsiloxane, poly- methyl alkyl siloxane, have
One or more mixture in machine modified polyorganosiloxane.
The plasticizer matrix of the present embodiment is obtained according to the following steps：
(i) it is esterified：The decanol for measuring is squeezed into into reactor by proportioning, temperature of reaction kettle adds the last of the ten Heavenly stems two after being less than 80 DEG C by proportioning
Acid, then, when material temperature rises to 220 DEG C, starts negative reaction by proportioning addition catalyst again, as acid number ＜ 0.1mgKOH/g,
Carry out flash distillation dealcoholysis；
(ii) refine：Flash distillation adds sodium carbonate to be neutralized after terminating by proportioning, neutralizes 10 minutes time, and temperature of reaction kettle rises to
When 200 DEG C, start stripping, then material temperature keeps 200 DEG C of stripping 2.5h, and cools down after being incubated half an hour, and adds by proportioning auxiliary
Material carries out refined stirring；
(iii) filter pressing is refined：Adjusting filter pump bypass valve makes the intrinsic pressure power of filter be maintained at 0.3Mpa, treats that filter pressing material is no and filters
In machine during pressure drop, terminate filter pressing；
(iv) distill：The vacuum system of molecular distillation equipment is opened, vacuum pump is run so that the vacuum of molecular distillation equipment system
Within reaching 100pa, heat conduction oil circulating pump is opened, the material inlet temperature for making molecular distillation equipment system is maintained at 175 DEG C, beats
The bottom valve of finished pot and the sample introduction valve of molecular distillation equipment system are opened, sample introduction frequency 30HZ, sample introduction flow is kept
0.7m3, open the separation reductor of molecular distillation equipment, be kept stirring for frequency for 40HZ, product in molecular distillation equipment from
Dynamic separating-purifying weight component, collects heavy constituent finished product, proceeds to finished pot storage.
Embodiment 2
The present embodiment is a kind of environmentally friendly low temperature resistant flame retardant composite elasticizer, including plasticizer matrix, plasticizer matrix by decanedioic acid,
Decanol, catalyst, sodium carbonate and adjuvant are through being esterified, refined, filter pressing is refined, distillation is obtained；The weight portion of decanedioic acid and decanol
Proportioning is：Decanedioic acid：1 part, decanol：3 parts；The addition of catalyst is the 0.6% of decanedioic acid and decanol gross weight, sodium carbonate
Addition is the 0.5% of decanedioic acid and decanol gross weight, and the addition of adjuvant is the 0.6% of decanedioic acid and decanol gross weight；Also wrap
Low temperature resistant flame retardant system is included, the addition of low temperature resistant flame retardant system is the 1.8% of plasticizer matrix weight；Low temperature resistant flame retardant system
The component of weight portion be configured to：Nano silicon：8.8 parts, fume colloidal silica：3.6 parts, Methyl Hydrogen Polysiloxane Fluid：72 parts,
Hydroxyl polydimethylsiloxane：9.8 parts, vinyltrimethoxy silane：4 parts, APP：6.6 parts, reactive diluent：1.6
Part, compatilizer：1.3 parts, coupling agent：0.6 part, levelling agent：1.3 parts, mixed chlorinated rare earth：0.2 part；Described nanometer titanium dioxide
The particle diameter of silicon is 25nm.
Wherein, catalyst is one or more mixing in isopropyl titanate, tetrabutyl titanate and p-methyl benzenesulfonic acid；Adjuvant
For kieselguhr or activated carbon；Reactive diluent is alkyl glycidyl ether, pungent certain herbaceous plants with big flowers acid glycidyl ester, trimethylolpropane tris
One or more mixture in glycidyl ether, toluene glycidyl ether, Oleum Ricini polyglycidyl ether；Compatilizer is
Maleic anhydride grafted PP；Coupling agent is vinyl tributyl ketoximyl silane coupling agent, methylvinyldichlorosilane
One or more mixture in coupling agent, methyl tributanoximo silane coupling agent；Levelling agent is isophorone, dipropyl
Keto-alcohol, fluorin modified crylic acid, phosphate modified acrylic acid, acrylic acid, polydimethylsiloxane, poly- methyl alkyl siloxane, have
One or more mixture in machine modified polyorganosiloxane.
The present embodiment plasticizer matrix is obtained according to the following steps：
(i) it is esterified：The decanol for measuring is squeezed into into reactor by proportioning, temperature of reaction kettle adds the last of the ten Heavenly stems two after being less than 80 DEG C by proportioning
Acid, then, when material temperature rises to 223 DEG C, starts negative reaction by proportioning addition catalyst again, as acid number ＜ 0.1mgKOH/g,
Carry out flash distillation dealcoholysis；
(ii) refine：Flash distillation adds sodium carbonate to be neutralized after terminating by proportioning, neutralizes 20 minutes time, and temperature of reaction kettle rises to
When 205 DEG C, start stripping, then material temperature keeps 205 DEG C of stripping 2.8h, and cools down after being incubated half an hour, and adds by proportioning auxiliary
Material carries out refined stirring；
(iii) filter pressing is refined：Adjusting filter pump bypass valve makes the intrinsic pressure power of filter be maintained at 0.4Mpa, treats that filter pressing material is no and filters
In machine during pressure drop, terminate filter pressing；
(iv) distill：The vacuum system of molecular distillation equipment is opened, vacuum pump is run so that the vacuum of molecular distillation equipment system
Within reaching 100pa, heat conduction oil circulating pump is opened, the material inlet temperature for making molecular distillation equipment system is maintained at 180 DEG C, beats
The bottom valve of finished pot and the sample introduction valve of molecular distillation equipment system are opened, sample introduction frequency 35HZ, sample introduction flow is kept
0.9m3, open the separation reductor of molecular distillation equipment, be kept stirring for frequency for 45HZ, product in molecular distillation equipment from
Dynamic separating-purifying weight component, collects heavy constituent finished product, proceeds to finished pot storage.
Embodiment 3
The present embodiment is a kind of environmentally friendly low temperature resistant flame retardant composite elasticizer, including plasticizer matrix, plasticizer matrix by decanedioic acid,
Decanol, catalyst, sodium carbonate and adjuvant are through being esterified, refined, filter pressing is refined, distillation is obtained；The weight portion of decanedioic acid and decanol
Proportioning is：Decanedioic acid：1 part, decanol：5 parts；The addition of catalyst is the 1% of decanedioic acid and decanol gross weight, sodium carbonate plus
Enter amount for the 0.7% of decanedioic acid and decanol gross weight, the addition of adjuvant is the 1% of decanedioic acid and decanol gross weight；Also include resistance to
Low-temperature flame retardant system, the addition of low temperature resistant flame retardant system is the 1.9% of plasticizer matrix weight；The weight of low temperature resistant flame retardant system
The component of amount part is configured to：Nano silicon：8.9 parts, fume colloidal silica：3.7 parts, Methyl Hydrogen Polysiloxane Fluid：73 parts, hydroxyl
Polydimethylsiloxane：9.9 parts, vinyltrimethoxy silane：5 parts, APP：6.7 parts, reactive diluent：1.7 parts,
Compatilizer：1.3 parts, coupling agent：0.7 part, levelling agent：1.4 parts, mixed chlorinated rare earth：0.3 part；Described nano silicon
Particle diameter be 30nm.
Wherein, catalyst is one or more mixing in isopropyl titanate, tetrabutyl titanate and p-methyl benzenesulfonic acid；Adjuvant
For kieselguhr or activated carbon；Reactive diluent is alkyl glycidyl ether, pungent certain herbaceous plants with big flowers acid glycidyl ester, trimethylolpropane tris
One or more mixture in glycidyl ether, toluene glycidyl ether, Oleum Ricini polyglycidyl ether；Compatilizer is
Maleic anhydride grafted PP；Coupling agent is vinyl tributyl ketoximyl silane coupling agent, methylvinyldichlorosilane
One or more mixture in coupling agent, methyl tributanoximo silane coupling agent；Levelling agent is isophorone, dipropyl
Keto-alcohol, fluorin modified crylic acid, phosphate modified acrylic acid, acrylic acid, polydimethylsiloxane, poly- methyl alkyl siloxane, have
One or more mixture in machine modified polyorganosiloxane.
The present embodiment plasticizer matrix is obtained according to the following steps：
(i) it is esterified：The decanol for measuring is squeezed into into reactor by proportioning, temperature of reaction kettle adds the last of the ten Heavenly stems two after being less than 80 DEG C by proportioning
Acid, then, when material temperature rises to 225 DEG C, starts negative reaction by proportioning addition catalyst again, as acid number ＜ 0.1mgKOH/g,
Carry out flash distillation dealcoholysis；
(ii) refine：Flash distillation adds sodium carbonate to be neutralized after terminating by proportioning, neutralizes 30 minutes time, and temperature of reaction kettle rises to
When 210 DEG C, start stripping, then material temperature keeps 210 DEG C of stripping 3h, and cools down after being incubated half an hour, and adds adjuvant by proportioning
Carry out refined stirring；
(iii) filter pressing is refined：Adjusting filter pump bypass valve makes the intrinsic pressure power of filter be maintained at 0.5Mpa, treats that filter pressing material is no and filters
In machine during pressure drop, terminate filter pressing；
(iv) distill：The vacuum system of molecular distillation equipment is opened, vacuum pump is run so that the vacuum of molecular distillation equipment system
Within reaching 100pa, heat conduction oil circulating pump is opened, the material inlet temperature for making molecular distillation equipment system is maintained at 185 DEG C, beats
The bottom valve of finished pot and the sample introduction valve of molecular distillation equipment system are opened, sample introduction frequency 40HZ, sample introduction flow is kept
1.2m3, open the separation reductor of molecular distillation equipment, be kept stirring for frequency for 50HZ, product in molecular distillation equipment from
Dynamic separating-purifying weight component, collects heavy constituent finished product, proceeds to finished pot storage.
In addition to the implementation, the present invention can also have other embodiment.All employing equivalents or equivalent transformation shape
Into technical scheme, all fall within the protection domain of application claims.
Claims (7)
1. a kind of environmentally friendly low temperature resistant flame retardant composite elasticizer, it is characterised in that：Including plasticizer matrix, the plasticizer matrix by
Decanedioic acid, decanol, catalyst, sodium carbonate and adjuvant are through being esterified, refined, filter pressing is refined, distillation is obtained；The decanedioic acid and the last of the ten Heavenly stems
The weight of alcohol is：Decanedioic acid：1 part, decanol：1.57-5 part；The addition of the catalyst is that decanedioic acid and decanol are total
The 0.2-1% of weight, the addition of the sodium carbonate is decanedioic acid and the 0.1-0.7% of decanol gross weight, the addition of the adjuvant
Measure as the 0.3-1% of decanedioic acid and decanol gross weight；Also include low temperature resistant flame retardant system, the addition of the low temperature resistant flame retardant system
Measure as the 1.7-1.9% of the plasticizer matrix weight；The component of the weight portion of the low temperature resistant flame retardant system is configured to：Nanometer
Silicon dioxide：8.7-8.9 part, fume colloidal silica：3.5-3.7 part, Methyl Hydrogen Polysiloxane Fluid：71-73 parts, hydroxyl poly dimethyl silicon
Oxygen alkane：9.7-9.9 part, vinyltrimethoxy silane：3-5 parts, APP：6.5-6.7 part, reactive diluent：1.5-1.7
Part, compatilizer：1.2-1.3 part, coupling agent：0.5-0.7 parts, levelling agent：1.2-1.4 part, mixed chlorinated rare earth：0.1-0.3 parts；
The particle diameter of described nano silicon is 20-30nm.
2. environmental protection low temperature resistant flame retardant composite elasticizer as claimed in claim 1, it is characterised in that：The catalyst is that metatitanic acid is different
One or more mixing in propyl ester, tetrabutyl titanate and p-methyl benzenesulfonic acid；The adjuvant is kieselguhr or activated carbon.
3. environmental protection low temperature resistant flame retardant composite elasticizer as claimed in claim 1, it is characterised in that：The reactive diluent is alkane
Base glycidyl ether, pungent certain herbaceous plants with big flowers acid glycidyl ester, trihydroxymethylpropanyltri diglycidyl ether, toluene glycidyl ether, Oleum Ricini
One or more mixture in polyglycidyl ether；The compatilizer is maleic anhydride grafted PP；It is described
Coupling agent is vinyl tributyl ketoximyl silane coupling agent, methylvinyldichlorosilane coupling agent, methyl tributanoximo silicon
One or more mixture in alkane coupling agent；The levelling agent be isophorone, DAA, fluorin modified crylic acid,
In phosphate modified acrylic acid, acrylic acid, polydimethylsiloxane, poly- methyl alkyl siloxane, organic modified polyorganosiloxane
One or more mixture.
4. the environmentally friendly low temperature resistant flame retardant composite elasticizer as described in claim 1-3 any claim, it is characterised in that：It is described
Plasticizer matrix is obtained according to the following steps：
(i) it is esterified：The decanol for measuring is squeezed into into reactor by proportioning, temperature of reaction kettle adds the last of the ten Heavenly stems two after being less than 80 DEG C by proportioning
Acid, then, when material temperature rises to 220-225 DEG C, starts negative reaction, as acid number ＜ by proportioning addition catalyst again
0.1mgKOH/g, carries out flash distillation dealcoholysis；
(ii) refine：Flash distillation adds sodium carbonate to be neutralized after terminating by proportioning, neutralizes minute time 10-30, temperature of reaction kettle liter
During to 200-210 DEG C, start stripping, then material temperature keeps 200-210 DEG C of stripping 2.5-3h, and cools down after being incubated half an hour, and
Adjuvant is added to carry out refined stirring by proportioning；
(iii) filter pressing is refined：Adjust filter pump bypass valve make the intrinsic pressure power of filter be maintained at 0.3～0.5Mpa, treat filter pressing material without and
In filter during pressure drop, terminate filter pressing；
(iv) distill：The vacuum system of molecular distillation equipment is opened, vacuum pump is run so that the vacuum of molecular distillation equipment system
Within reaching 100pa, heat conduction oil circulating pump is opened, the material inlet temperature for making molecular distillation equipment system is maintained at 175-185
DEG C, the bottom valve of finished pot and the sample introduction valve of molecular distillation equipment system are opened, sample introduction 35 ± 5HZ of frequency is kept, enter
Sample flow 0.7m3-1.2m3, the separation reductor of molecular distillation equipment is opened, it is 45 ± 5HZ to be kept stirring for frequency, and product is dividing
Purification weight component is automatically separated in sub- distillation equipment, heavy constituent finished product is collected, finished pot storage is proceeded to.
5. the environmentally friendly low temperature resistant flame retardant composite elasticizer as described in claim 1-3 any claim, it is characterised in that：Including
Plasticizer matrix, the plasticizer matrix is by decanedioic acid, decanol, catalyst, sodium carbonate and adjuvant through esterification, refined, filter pressing
Refined, distillation is obtained；The weight of the decanedioic acid and decanol is：Decanedioic acid：1 part, decanol：1.57 part；The catalysis
The addition of agent is the 0.2% of decanedioic acid and decanol gross weight, and the addition of the sodium carbonate is decanedioic acid and decanol gross weight
0.1%, the addition of the adjuvant is the 0.3% of decanedioic acid and decanol gross weight；Also include low temperature resistant flame retardant system, it is described resistance to low
The addition of warm flame-retardant system is the 1.7% of the plasticizer matrix weight；The component of the weight portion of the low temperature resistant flame retardant system
It is configured to：Nano silicon：8.7 parts, fume colloidal silica：3.5 parts, Methyl Hydrogen Polysiloxane Fluid：71 parts, hydroxyl poly dimethyl silicon
Oxygen alkane：9.7 parts, vinyltrimethoxy silane：3 parts, APP：6.5 parts, reactive diluent：1.5 parts, compatilizer：1.2
Part, coupling agent：0.5 part, levelling agent：1.2 parts, mixed chlorinated rare earth：0.1 part；The particle diameter of described nano silicon is
20nm。
6. the environmentally friendly low temperature resistant flame retardant composite elasticizer as described in claim 1-3 any claim, it is characterised in that：Including
Plasticizer matrix, the plasticizer matrix is by decanedioic acid, decanol, catalyst, sodium carbonate and adjuvant through esterification, refined, filter pressing
Refined, distillation is obtained；The weight of the decanedioic acid and decanol is：Decanedioic acid：1 part, decanol：3 parts；The catalyst
Addition is the 0.6% of decanedioic acid and decanol gross weight, and the addition of the sodium carbonate is decanedioic acid and decanol gross weight
0.5%, the addition of the adjuvant is the 0.6% of decanedioic acid and decanol gross weight；Also include low temperature resistant flame retardant system, it is described resistance to low
The addition of warm flame-retardant system is the 1.8% of the plasticizer matrix weight；The component of the weight portion of the low temperature resistant flame retardant system
It is configured to：Nano silicon：8.8 parts, fume colloidal silica：3.6 parts, Methyl Hydrogen Polysiloxane Fluid：72 parts, hydroxyl poly dimethyl silicon
Oxygen alkane：9.8 parts, vinyltrimethoxy silane：4 parts, APP：6.6 parts, reactive diluent：1.6 parts, compatilizer：1.3
Part, coupling agent：0.6 part, levelling agent：1.3 parts, mixed chlorinated rare earth：0.2 part；The particle diameter of described nano silicon is
25nm。
7. the environmentally friendly low temperature resistant flame retardant composite elasticizer as described in claim 1-3 any claim, it is characterised in that：Including
Plasticizer matrix, the plasticizer matrix is by decanedioic acid, decanol, catalyst, sodium carbonate and adjuvant through esterification, refined, filter pressing
Refined, distillation is obtained；The weight of the decanedioic acid and decanol is：Decanedioic acid：1 part, decanol：5 parts；The catalyst
Addition is the 1% of decanedioic acid and decanol gross weight, and the addition of the sodium carbonate is the 0.7% of decanedioic acid and decanol gross weight,
The addition of the adjuvant is the 1% of decanedioic acid and decanol gross weight；Also include low temperature resistant flame retardant system, the low temperature resistant flame retardant
The addition of system is the 1.9% of the plasticizer matrix weight；The component of the weight portion of the low temperature resistant flame retardant system is constituted
For：Nano silicon：8.9 parts, fume colloidal silica：3.7 parts, Methyl Hydrogen Polysiloxane Fluid：73 parts, hydroxyl polydimethylsiloxanes
Alkane：9.9 parts, vinyltrimethoxy silane：5 parts, APP：6.7 parts, reactive diluent：1.7 parts, compatilizer：1.3
Part, coupling agent：0.7 part, levelling agent：1.4 parts, mixed chlorinated rare earth：0.3 part；The particle diameter of described nano silicon is
30nm。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611066284.XA CN106589466A (en) | 2016-11-28 | 2016-11-28 | Environment-friendly low-temperature-resistant fire-retardant complex plasticizer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611066284.XA CN106589466A (en) | 2016-11-28 | 2016-11-28 | Environment-friendly low-temperature-resistant fire-retardant complex plasticizer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106589466A true CN106589466A (en) | 2017-04-26 |
Family
ID=58593621
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611066284.XA Pending CN106589466A (en) | 2016-11-28 | 2016-11-28 | Environment-friendly low-temperature-resistant fire-retardant complex plasticizer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106589466A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102351692A (en) * | 2011-10-10 | 2012-02-15 | 山东天兴生物科技有限公司 | Preparation method for dimethyl sebacate |
| CN105272850A (en) * | 2014-07-09 | 2016-01-27 | 江苏森禾化工科技有限公司 | High and low temperature-resistant low-fogging degree functional environment-friendly plasticizer |
-
2016
- 2016-11-28 CN CN201611066284.XA patent/CN106589466A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102351692A (en) * | 2011-10-10 | 2012-02-15 | 山东天兴生物科技有限公司 | Preparation method for dimethyl sebacate |
| CN105272850A (en) * | 2014-07-09 | 2016-01-27 | 江苏森禾化工科技有限公司 | High and low temperature-resistant low-fogging degree functional environment-friendly plasticizer |
Non-Patent Citations (3)
| Title |
|---|
| 陈涛，等: "甲基含氢硅油表面改性无卤膨胀阻燃剂研究", 《塑料助剂》 * |
| 马雪琴，等: "低温增塑剂癸二酸二异辛酯的合成研究", 《塑料工业》 * |
| 鲁凤兰: "无毒增塑剂的生产与应用", 《精细石油化工进展》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101279212B (en) | Preparation of intercrossed network water dealcoholizing pervaporation membrane | |
| CN105585854B (en) | A kind of high-viscosity modified asphalt and preparation method thereof for being easy to construct | |
| CN106164164A (en) | Vinyl chloride resin plasticizer containing non-phthalic acid system ester and the vinyl chloride resin composition containing this plasticizer | |
| CN105440547A (en) | High-strength heat-resistant polyethylene tube material | |
| CN106519698A (en) | High-temperature-resistant compound plasticizer | |
| CN104178022B (en) | Preparation method of heat-resistant imporous enameled wire insulating paint for high speed machines | |
| CN106751446A (en) | A kind of blower fan high intensity friction resistance material | |
| WO2011131153A1 (en) | Polymer type phosphor-containing flame retardant, preparation method and application thereof | |
| CN103665248A (en) | Phosphorus-silicon flame retardant resin and preparation method thereof | |
| CN102167920B (en) | Aqueous flame-retardant coating and preparation method thereof | |
| CN104448830A (en) | Phosphorus-silicon composite flame retardant as well as preparation method and application thereof | |
| CN106751876A (en) | A kind of production method of high temperature resistant composite elasticizer | |
| CN102140115B (en) | Flame-retardant plasticizer of methyl silicate trichloroethyl ester compound and preparation method thereof | |
| CN106589466A (en) | Environment-friendly low-temperature-resistant fire-retardant complex plasticizer | |
| CN106497070A (en) | A kind of production method of environmental protection low temperature resistant flame retardant composite elasticizer | |
| CN107540550A (en) | A kind of high-efficiency synthesis method of trioctyl trimellitate (TOTM) | |
| CN107022111A (en) | A kind of response type light stabilizer and preparation method thereof | |
| CN106317764B (en) | A kind of method of modifying improving phenolic resin toughness and anti-flammability | |
| CN101565431A (en) | Process for synthetizing phosphoester oligopolymer BDP | |
| CN109722028A (en) | Addition-type silicon rubber | |
| CN106589950A (en) | Production method for high-strength linear composite plasticizer | |
| CN106497071A (en) | A kind of high strength linear composite elasticizer | |
| CN108218700A (en) | A kind of automotive upholstery specialty plasticiser TM8 | |
| CN103804692A (en) | Preparation method of phosphonate flame retardant containing high phosphorus content and applying to polyurethane foam | |
| CN109369699B (en) | Reactive organosilicon flame retardant allyl silicic acid trisilacyl alcohol ester compound and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170426 |