CN110483943A - A kind of polyacetal composition and preparation method thereof - Google Patents
A kind of polyacetal composition and preparation method thereof Download PDFInfo
- Publication number
- CN110483943A CN110483943A CN201910851099.9A CN201910851099A CN110483943A CN 110483943 A CN110483943 A CN 110483943A CN 201910851099 A CN201910851099 A CN 201910851099A CN 110483943 A CN110483943 A CN 110483943A
- Authority
- CN
- China
- Prior art keywords
- auxiliary agent
- polyacetals
- polyacetal composition
- acid
- diisocyanate
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/003—Polymeric products of isocyanates or isothiocyanates with epoxy compounds having no active hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L59/00—Compositions of polyacetals; Compositions of derivatives of polyacetals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/24—Crystallisation aids
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
Abstract
The present invention provides a kind of polyacetal compositions and preparation method thereof, and wherein polyacetal composition includes polyacetals and auxiliary agent；The mass ratio of the polyacetals and auxiliary agent is 1000:1~100:1；The auxiliary agent is copolymerized by cyclic ethers and/or cyclic acetal with isocyanate ester compound.The preparation method of polyacetal composition includes: that cyclic ethers and/or cyclic acetal, isocyanate ester compound, catalyst are blended, and auxiliary agent is prepared；By polyacetals and auxiliary agent melting mixing, the polyacetal composition is prepared.Polyacetal composition prepared by the present invention had both had improved crystal property, the thermal stability of polyacetals also can be improved, and structural compatibility is good, is conducive to evenly dispersed.
Description
Technical field
The present invention relates to a kind of polyacetal compositions more particularly to a kind of polyacetal composition and preparation method thereof, belong to
Technical field of polymer materials.
Background technique
Polyacetals is important one of engineering plastics, excellent self-lubricating, resistance to tired because it is with intensity outstanding and rigidity
The performances such as labor and wearability, are widely used in the industries such as automobile, instrument, electronic apparatus.
Usually there is the problems such as brittleness is big, shrinking percentage is high and processing thermal decomposition in polyacetals, these problems can pass through addition
The auxiliary agents such as nucleating agent and heat stabilizer are improved.Polyacetals crystalline rate and crystallization temperature can be improved in nucleating agent, and refinement is brilliant
Grain, and then shrinking percentage is reduced, product size stability is improved, meanwhile, the raising of crystalline rate is also conducive to shorten machine-shaping week
Phase.Heat stabilizer, which is added, can inhibit the thermal decomposition problem in polyacetals process.
Common nucleating agent includes organic low molecular class (melamine formal, glycidyl ether trimethoxy silane
Deng), inorganic species (talcum powder, montmorillonite, diatomite, boron nitride, nano zirconium dioxide etc.), organic polymer class (polyamide,
Kynoar, polytetrafluoroethylene (PTFE) etc.) and compound system (polyester compounds nanometer calcium carbonate etc.).However, organic low molecular class at
Core agent fusing point is low, and stability is poor in product processing；Inorganic nucleating agent has that compatibility is bad, bad dispersibility；
And existing organic polymer class and compound system nucleating agent can not improve asking for polyacetals thermal stability there is also having a single function
Topic, therefore the high-contents auxiliary agent such as generally require into system while adding antioxidant, acid absorbent, processing stabilizers guarantees to gather
The production cost of product is greatly improved in the thermal stability of acetal process.For example, Chinese patent CN102516706B is reported
The crystal property and stability of polyacetals are taken into account using three kinds of composite nucleating agent, antioxidant and stabilizer auxiliary agents in road simultaneously,
Not only make the modified technique of polyacetals relative complex, but also each analog assistant price general charged is higher, increase modified polyacetal at
This.
Summary of the invention
The technical problem to be solved by the present invention is to regulate and control the crystallization behavior of polyacetals by a kind of auxiliary agent, while improving its heat
Stability.
In order to solve the above technical problems, one aspect of the present invention, be to provide one kind have both rapid crystallization performance and
The polyacetal composition of high thermal stability, it includes polyacetals and a kind of auxiliary agent, the auxiliary agent be cyclic ethers and/or cyclic acetal with
The copolymer of isocyanate compound；A kind of preparation method of polyacetal composition is also provided, is prepared by this method
Polyacetal composition is with rapid crystallization performance and high thermal stability.
To achieve the above object, the technical solution adopted in the present invention is as follows:
A kind of polyacetal composition, including polyacetals and auxiliary agent；The mass ratio of the polyacetals and auxiliary agent be 1000:1~
100:1；Preferably, the mass ratio of the polyacetals and auxiliary agent is 300:1~800:1；
The auxiliary agent is copolymerized by cyclic ethers and/or cyclic acetal with isocyanate ester compound.
Further, the auxiliary agent be cyclic ethers and/or cyclic acetal and isocyanate ester compound under the action of catalyst
Copolymer.
The catalyst is lewis acid or nonvolatile Bronsted acid；Preferably, the catalyst is boron trifluoride ether
One of complex compound, boron trifluoride ether complex, heteropoly acid, isopolyacid, heteropoly acid acid salt and isopolyacid acid salt or
It is several.
The heteropoly acid is preferably silico-tungstic acid, silicomolybdic acid, phosphomolybdic acid, phosphotungstic acid, P-Mo-Wo acid, molybdovanaphosphoric acid, phosphorus tungsten vanadium
Acid；
The isopolyacid is preferably metamolybdic acid, para-molybdic acid, metatungstic acid, para-tungstic acid, metavanadic acid, secondary vanadic acid.
The molar ratio of the cyclic ethers and/or cyclic acetal, isocyanate ester compound is 1000:1~10.
The molar ratio of the catalyst, cyclic ethers and/or cyclic acetal is 1~80ppm (ppm is million scores, dimensionless).
The catalyst nonactive organic solvent diluting or dissolution, the organic solvent are selected from n-hexane, normal heptane, ring
At least one of hexane, formic acid, acetic acid, ethyl acetate, methyl formate.
The cyclic ethers is one or more of following compound: ethylene oxide, propylene oxide, epoxy butane, epoxide ring
Hexane, oxetanes, 1,3- dioxolane, 1,3,5- trioxane；
The cyclic acetal is one or more of following compound: propylene glycol, diethylene glycol formal, three
Ethylene glycol acetal, 1,4- butylene glycol formal, 1,5- pentanediol formal, 1,6- butylene glycol formal.
The isocyanate ester compound is aliphatic or aromatic polyisocyanate, preferably toluene di-isocyanate(TDI)
(TDI), methyl diphenylene diisocyanate (MDI), hexamethylene diisocyanate (HDI) or its autopolymer, to two isocyanide of benzene
Acid esters (PPDI), 1,5- naphthalene diisocyanate (NDI), 3,3 '-dimethyl diphenyl diisocyanate (TODI), dicyclohexyl methyl hydride
Diisocyanate (HMDI) and one or more of isophorone diisocyanate (IPDI) or its autopolymer.
The polyacetals is the pellet or powder for being copolymerized acetal or equal polyacetals, preferably in 190 DEG C, 2.16kg loading condiction
Lower melt flow rate (MFR) is 6~27g/10min pellet or powder.
A kind of preparation method of polyacetal composition, which comprises the following steps:
Cyclic ethers and/or cyclic acetal, isocyanate ester compound, catalyst are blended, auxiliary agent is prepared；
By polyacetals and auxiliary agent melting mixing, the polyacetal composition is prepared.
The equipment that the polyacetals and auxiliary agent melting mixing use is single screw extrusion machine, double screw extruder, mixer
Or twin-roll machine；The temperature of the polyacetals and auxiliary agent melting mixing is 170~200 DEG C.
The invention has the benefit that
1) auxiliary agent and polyacetals are polarity organic polymers, and structural compatibility is good, just can be equal without coupling agent
Even dispersion, conducive to the simplification of production technology and the reduction of product cost；
2) polyacetal composition after adding auxiliary agent has improved crystal property, and crystallization temperature and crystallization speed can be improved
Rate, and reduce molding shrinkage；
3) polyacetal composition after adding auxiliary agent has both the thermal stability being improved.
Specific embodiment
Below by specific embodiment, the present invention will be further described, and embodiment of the present invention is intended only as to this hair
Bright explanation, does not limit the scope of the invention.
Each raw material sources are as follows in embodiment:
1,3,5- trioxane is Aladdin Reagent Company product, and analysis is pure, and No. CAS is 110-88-3；
1,3- dioxolane is Aladdin Reagent Company product, and analysis is pure, and No. CAS is 646-06-0；
1,4-butanediol formal is Mai Ruier chemical company product, and No. CAS is 505-65-7；
7-oxa-bicyclo[4.1.0 is Aladdin Reagent Company product, and No. CAS is 286-20-4；
Boron trifluoride ether complex is Tokyo Chemical Industry Co., Ltd's product, containing about 30% boron trifluoride, No. CAS
For 593-04-4；
Boron trifluoride etherate is Tokyo Chemical Industry Co., Ltd's product, containing about 30% boron trifluoride, No. CAS
For 109-63-7；
N-hexane is Aladdin Reagent Company product, and No. CAS is 110-54-3；
Methyl formate is Xilong Chemical Co., Ltd's product, and No. CAS is 107-31-3；
Phosphotungstic acid is Aladdin Reagent Company product, and No. CAS is 12501-23-4；
Phosphomolybdic acid is Wei Ao chemical company product, and No. CAS is 11104-88-4；
Oxetanes is Aladdin Reagent Company product, and No. CAS is 503-30-0；
Propylene glycol is Mai Ruier chemical company product, and No. CAS is 505-22-6；
Paraphenylene diisocyanate is Mai Ruier chemical company product, and No. CAS is 104-49-4；
Formic acid is Xilong Chemical Co., Ltd's product, and No. CAS is 64-18-6；
Hexamethylene is Xilong Chemical Co., Ltd, and analysis is pure, and No. CAS is 110-82-7；
Methyl diphenylene diisocyanate (MDI) is Wan Hua chemical company product, and No. CAS is 101-68-8；
Hexamethylene diisocyanate (HDI) and its tripolymer are Wan Hua chemical company products, and No. CAS of HDI is 822-
06-0；
Toluene di-isocyanate(TDI) (TDI) is Wan Hua chemical company product, and No. CAS is 26471-62-5；
Dicyclohexyl methyl hydride diisocyanate (HMDI) is ten thousand magnificent Products, and No. CAS is 5124-30-1；
Isophorone diisocyanate (IPDI) is ten thousand magnificent Products, and No. CAS is 4098-71-9；
Diatomite is Aladdin Reagent Company product, and No. CAS is 91053-39-3；
Calcium stearate is Aladdin Reagent Company product, and No. CAS is 1592-23-0；
Other materials, reagent are commercially available without specified otherwise.
[embodiment 1]
The preparation of auxiliary agent A:
Spare (the wt% expression quality percentage of concentration that boron trifluoride ether complex is diluted to 1wt% with hexamethylene
Than), 1,3,5- trioxane is then heated to 70 DEG C, after melting completely, is removed water and is filtered with molecular sieve；After diluting
Boron trifluoride ether complex be quickly uniformly mixed with 1,3,5- trioxanes after purification, control reaction temperature is 80
DEG C, when system occurs muddy, methyl diphenylene diisocyanate is added, wherein boron trifluoride ether complex and 1,3,5-
The molar ratio of trioxane is 10ppm, methyl diphenylene diisocyanate and 1, the molar ratio of 3,5- trioxanes
For 10:1000；After system is fully cured, dry reaction product is crushed, auxiliary agent A is made.
The preparation of polyacetal composition:
(1) polyacetals is dried in vacuo；
(2) by after drying polyacetals and auxiliary agent A according to 500:1 mass ratio mix, melted in double screw extruder
It is kneaded；Control screw speed is 200rpm, and extruder front-end temperature is 170 DEG C, and middle section temperature is 185 DEG C, and back segment temperature is 170
DEG C, cooling temperature is 35 DEG C；
(3) material after discharging in extruder, be down to crystallizing at room temperature, obtain polyacetal composition by water cooled tie rod pelletizing；
(4) by after the vacuum drying of above-mentioned polyacetal composition, standard batten is got with injection molding machine, is characterized and is crystallized by DSC
Behavior characterizes thermal stability by TGA, using vernier caliper measurement shrinking percentage.Test result is as shown in table 1.
[embodiment 2]
The preparation of auxiliary agent B:
Phosphotungstic acid is dissolved with methyl formate, the concentration for being made into 0.15wt% is spare (wt% indicates mass percent), so
1,3,5- trioxane is heated to 70 DEG C afterwards, after melting completely, is removed water and is filtered with molecular sieve；Successively in the reactor
Salkowski's solution, after purification 1,3,5- trioxanes and 1 is added, 3- dioxolane is quickly uniformly mixed, control
Reaction temperature is 80 DEG C, and when system occurs muddy, the hexamethylene diisocyanate after melting is added, wherein monomer 1,3,
5- trioxane and comonomer 1, the molar ratio of 3- dioxolane are 25:1, mole of phosphotungstic acid and two kinds of monomers
Than for 2ppm, the molar ratio of hexamethylene diisocyanate and two kinds of monomers is controlled in 5:1000；After system is fully cured, powder
Auxiliary agent B is made in broken dry reaction product.
The preparation of polyacetal composition:
(1) polyacetals is dried in vacuo；
(2) by after drying polyacetals and auxiliary agent B according to 100:1 mass ratio mix, melted in double screw extruder
It is kneaded；Control screw speed is 200rpm, and extruder front-end temperature is 185 DEG C, and middle section temperature is 200 DEG C, and back segment temperature is 185
DEG C, cooling temperature is 35 DEG C；
(3) material after discharging in extruder, be down to crystallizing at room temperature, obtain polyacetal composition by water cooled tie rod pelletizing；
(4) by after the vacuum drying of above-mentioned polyacetal composition, standard batten is got with injection molding machine, is characterized and is crystallized by DSC
Behavior characterizes thermal stability by TGA, using vernier caliper measurement shrinking percentage.Test result is as shown in table 1.
[embodiment 3]
The preparation of auxiliary agent C:
Spare (the wt% expression quality percentage of concentration that boron trifluoride etherate is diluted to 1wt% with n-hexane
Than), 1,3,5- trioxane is then heated to 70 DEG C, after melting completely, is removed water and is filtered with molecular sieve；Successively anti-
Answer the boron trifluoride etherate after dilution is added in device, after purification 1,3,5- trioxanes and 1,4-butanediol contracting
Formaldehyde is quickly uniformly mixed, and control reaction temperature is 80 DEG C, and when system occurs muddy, two isocyanide of dicyclohexyl methyl hydride is added
Acid esters, wherein the molar ratio of monomer 1,3,5- trioxane and comonomer 1,4-butanediol formal is 25:1, trifluoro
The molar ratio for changing diethyl etherate and two kinds of monomers is 20ppm, and dicyclohexyl methyl hydride diisocyanate rubs with two kinds of monomers
You are than being 1:1000；After system is fully cured, dry reaction product is crushed, auxiliary agent C is made.
The preparation of polyacetal composition:
(1) polyacetals is dried in vacuo；
(2) by after drying polyacetals and auxiliary agent C according to 200:1 mass ratio mix, melted in double screw extruder
It is kneaded；Control screw speed is 200rpm, and extruder front-end temperature is 175 DEG C, and middle section temperature is 190 DEG C, and back segment temperature is 175
DEG C, cooling temperature is 35 DEG C；
(3) material after discharging in extruder, be down to crystallizing at room temperature, obtain polyacetal composition by water cooled tie rod pelletizing；
(4) by after the vacuum drying of above-mentioned polyacetal composition, standard batten is got with injection molding machine, is characterized and is crystallized by DSC
Behavior characterizes thermal stability by TGA, using vernier caliper measurement shrinking percentage.Test result is as shown in table 1.
[embodiment 4]
The preparation of auxiliary agent D:
The dissolution of phosphomolybdic acid formic acid is made into the solution for standby of 0.15wt% (wt% indicates mass percent)；By phosphomolybdic acid
Solution is quickly uniformly mixed with 7-oxa-bicyclo[4.1.0, and control reaction temperature is 80 DEG C, and when system occurs muddy, equimolar ratio is added
Isophorone diisocyanate and toluene di-isocyanate(TDI), wherein the molar ratio of phosphomolybdic acid and 7-oxa-bicyclo[4.1.0 be 4ppm, institute
Molar ratio with two kinds of isocyanate species and 7-oxa-bicyclo[4.1.0 is 1:1000；After system is fully cured, dry reaction is crushed
Auxiliary agent D is made in product.
The preparation of polyacetal composition:
(1) polyacetals is dried in vacuo；
(2) by after drying polyacetals and auxiliary agent D according to 1000:1 mass ratio mix, melted in double screw extruder
It is kneaded；Control screw speed is 200rpm, and extruder front-end temperature is 170 DEG C, and middle section temperature is 185 DEG C, and back segment temperature is 170
DEG C, cooling temperature is 35 DEG C；
(3) material after discharging in extruder, be down to crystallizing at room temperature, obtain polyacetal composition by water cooled tie rod pelletizing；
(4) by after the vacuum drying of above-mentioned polyacetal composition, standard batten is got with injection molding machine, is characterized and is crystallized by DSC
Behavior characterizes thermal stability by TGA, using vernier caliper measurement shrinking percentage.Test result is as shown in table 1.
[embodiment 5]
The preparation of auxiliary agent E:
Spare (the wt% expression quality percentage of concentration that boron trifluoride ether complex is diluted to 1wt% with hexamethylene
Than), 1,3,5- trioxane is then heated to 70 DEG C, after melting completely, is removed water and is filtered with molecular sieve；After diluting
Boron trifluoride ether complex be quickly uniformly mixed with 1,3,5- trioxanes after purification, control reaction temperature is 80
DEG C, when system occurs muddy, isophorone diisocyanate is added, wherein boron trifluoride ether complex and 1,3,5- tri-
The molar ratio of oxinane is 80ppm, isophorone diisocyanate and the molar ratio of 1,3,5- trioxanes are 8:
1000；After system is fully cured, dry reaction product is crushed, auxiliary agent E is made.
The preparation of polyacetal composition:
(1) polyacetals is dried in vacuo；
(2) by after drying polyacetals and auxiliary agent E according to 300:1 mass ratio mix, melted in double screw extruder
It is kneaded；Control screw speed is 200rpm, and extruder front-end temperature is 175 DEG C, and middle section temperature is 190 DEG C, and back segment temperature is 175
DEG C, cooling temperature is 35 DEG C；
(3) material after discharging in extruder, be down to crystallizing at room temperature, obtain polyacetal composition by water cooled tie rod pelletizing；
(4) by after the vacuum drying of above-mentioned polyacetal composition, standard batten is got with injection molding machine, is characterized and is crystallized by DSC
Behavior characterizes thermal stability by TGA, using vernier caliper measurement shrinking percentage.Test result is as shown in table 1.
[embodiment 6]
The preparation of auxiliary agent F:
Boron trifluoride etherate is diluted to the concentration (wt% indicates mass percent) of 1wt% with n-hexane, according to
It is secondary that boron trifluoride etherate, oxetanes after diluting are added in the reactor, it is quickly uniformly mixed, control reaction is warm
Degree is 80 DEG C, and when system occurs muddy, hexamethylene diisocyanate trimer is added, wherein boron trifluoride ether complexing
The molar ratio of object and oxetanes is 50ppm, and the molar ratio of hexamethylene diisocyanate trimer and oxetanes is
6:1000；After system is fully cured, dry reaction product is crushed, auxiliary agent F is made.
The preparation of polyacetal composition:
(1) polyacetals is dried in vacuo；
(2) by after drying polyacetals and auxiliary agent F according to 800:1 mass ratio mix, melted in double screw extruder
It is kneaded；Control screw speed is 200rpm, and extruder front-end temperature is 170 DEG C, and middle section temperature is 185 DEG C, and back segment temperature is 170
DEG C, cooling temperature is 35 DEG C；
(3) material after discharging in extruder, be down to crystallizing at room temperature, obtain polyacetal composition by water cooled tie rod pelletizing；
(4) by after the vacuum drying of above-mentioned polyacetal composition, standard batten is got with injection molding machine, is characterized and is crystallized by DSC
Behavior characterizes thermal stability by TGA, using vernier caliper measurement shrinking percentage.Test result is as shown in table 1.
[embodiment 7]
The preparation of auxiliary agent G:
The dissolution of phosphotungstic acid methyl formate is made into the solution for standby of 0.15wt% (wt% indicates mass percent)；By phosphorus
Tungstic acid is quickly uniformly mixed with 7-oxa-bicyclo[4.1.0, and control reaction temperature is 80 DEG C, and when system occurs muddy, toluene is added
Diisocyanate, wherein the molar ratio of phosphotungstic acid and 7-oxa-bicyclo[4.1.0 is 3ppm, toluene di-isocyanate(TDI) used and epoxy hexamethylene
The molar ratio of alkane is 3:1000；After system is fully cured, dry reaction product is crushed, auxiliary agent G is made.
The preparation of polyacetal composition:
(1) polyacetals is dried in vacuo；
(2) by after drying polyacetals and auxiliary agent G according to 900:1 mass ratio mix, melted in double screw extruder
It is kneaded；Control screw speed is 200rpm, and extruder front-end temperature is 180 DEG C, and middle section temperature is 195 DEG C, and back segment temperature is 180
DEG C, cooling temperature is 35 DEG C；
(3) material after discharging in extruder, be down to crystallizing at room temperature, obtain polyacetal composition by water cooled tie rod pelletizing；
(4) by after the vacuum drying of above-mentioned polyacetal composition, standard batten is got with injection molding machine, is characterized and is crystallized by DSC
Behavior characterizes thermal stability by TGA, using vernier caliper measurement shrinking percentage.Test result is as shown in table 1.
[embodiment 8]
The preparation of auxiliary agent H:
The dissolution of phosphomolybdic acid formic acid is made into the solution for standby of 0.15wt% (wt% indicates mass percent)；By phosphomolybdic acid
Solution is quickly uniformly mixed with propylene glycol, and control reaction temperature is 100 DEG C, when system occurs muddy, is added and is melted
Paraphenylene diisocyanate afterwards, wherein the molar ratio of phosphomolybdic acid and propylene glycol is 1ppm, paraphenylene diisocyanate used
Molar ratio with propylene glycol is 2:1000；After system is fully cured, dry reaction product is crushed, auxiliary agent H is made.
The preparation of polyacetal composition:
(1) polyacetals is dried in vacuo；
(2) by after drying polyacetals and auxiliary agent H according to 600:1 mass ratio mix, melted in double screw extruder
It is kneaded；Control screw speed is 200rpm, and extruder front-end temperature is 170 DEG C, and middle section temperature is 185 DEG C, and back segment temperature is 170
DEG C, cooling temperature is 35 DEG C；
(3) material after discharging in extruder, be down to crystallizing at room temperature, obtain polyacetal composition by water cooled tie rod pelletizing；
(4) by after the vacuum drying of above-mentioned polyacetal composition, standard batten is got with injection molding machine, is characterized and is crystallized by DSC
Behavior characterizes thermal stability by TGA, using vernier caliper measurement shrinking percentage.Test result is as shown in table 1.
[embodiment 9]
The preparation of pure polyacetals:
(1) polyacetals is dried in vacuo；
(2) polyacetals after drying is put into double screw extruder, screw speed 200rpm, extruder front-end temperature
It is 170 DEG C, middle section temperature is 185 DEG C, and back segment temperature is 170 DEG C, and cooling temperature is 35 DEG C；
(3) material after discharging in extruder, be down to crystallizing at room temperature, obtain pure polyacetals by water cooled tie rod pelletizing；
(4) by after the vacuum drying of pure polyacetals, standard batten is got with injection molding machine, crystallization behavior is characterized by DSC, is passed through
TGA characterizes thermal stability, using vernier caliper measurement shrinking percentage.The results are shown in Table 1.
[embodiment 10]
Add the preparation of the polyacetal composition of nucleating agent:
(1) polyacetals is dried in vacuo；
(2) by after drying polyacetals and nucleating agent diatomite according to mass ratio 200:1 after mixing, put into twin-screw
Melting mixing in extruder, control screw speed are 200rpm, and extruder front-end temperature is 185 DEG C, and middle section temperature is 200 DEG C,
Back segment temperature is 185 DEG C, and cooling temperature is 35 DEG C；
(3) material after mixing is discharged from extruder, water cooled tie rod pelletizing after being down to crystallizing at room temperature, obtains bunching
Aldehyde compositions；
(4) by after the vacuum drying of above-mentioned polyacetal composition, standard batten is got with injection molding machine, is characterized and is crystallized by DSC
Behavior characterizes thermal stability by TGA, using vernier caliper measurement shrinking percentage.The results are shown in Table 1.
[embodiment 11]
Add the preparation of the polyacetal composition of heat stabilizer:
(1) polyacetals is dried in vacuo；
(2) by after drying polyacetals and heat stabilizer calcium stearate according to mass ratio 200:1 after mixing, investment is double
Melting mixing in screw extruder, control screw speed are 200rpm, and extruder front-end temperature is 180 DEG C, and middle section temperature is 195
DEG C, back segment temperature is 180 DEG C, and cooling temperature is 35 DEG C；
(3) material after mixing is discharged from extruder, water cooled tie rod pelletizing after being down to crystallizing at room temperature, obtains bunching
Aldehyde compositions；
(4) by after the vacuum drying of above-mentioned polyacetal composition, standard batten is got with injection molding machine, is characterized and is crystallized by DSC
Behavior characterizes thermal stability by TGA, using vernier caliper measurement shrinking percentage.The results are shown in Table 1.
[embodiment 12]
Add the preparation of the polyacetal composition of nucleating agent and heat stabilizer:
(1) polyacetals is dried in vacuo；
(2) by after drying polyacetals and nucleating agent diatomite, heat stabilizer calcium stearate mix according to mass ratio 200:1:1
After closing uniformly, melting mixing in double screw extruder is put into, control screw speed is 200rpm, and extruder front-end temperature is 175
DEG C, middle section temperature is 190 DEG C, and back segment temperature is 175 DEG C, and cooling temperature is 35 DEG C；
(3) material after mixing is discharged from extruder, water cooled tie rod pelletizing after being down to crystallizing at room temperature, obtains bunching
Aldehyde compositions；
(4) by after polyacetal composition obtained vacuum drying, standard batten is got with injection molding machine, is characterized and is tied by DSC
Brilliant behavior characterizes thermal stability by TGA, using vernier caliper measurement shrinking percentage.The results are shown in Table 1.
The crystallization behavior of polyacetal composition or pure polyacetals in above-described embodiment passes through differential scanning calorimetry instrument
(DSC is purchased from Switzerland METTLER TOLEDO company) characterizes, sample quality 8-10mg, under nitrogen atmosphere, with 20 DEG C/min heating
Rate is warming up to 200 DEG C, constant temperature 5min, is then cooled to 50 DEG C with the rate of 20 DEG C/min, records crystallization process curve, and remember
It records crystallization initiation temperature, terminate crystallization temperature, peak crystallization temperature (Tpc) and flexible chain (t1/2).Flexible chain falls
Number can reflect the crystalline rate under experimental temperature.
Thermogravimetric analysis uses thermogravimetric analyzer (TGA is purchased from Switzerland METTLER TOLEDO company), sample quality 8-
10mg, nitrogen atmosphere, 10 DEG C/min of heating rate.Under thermogravimetric (TG) curve record constant heating rates sintering sample weight loss with temperature change
Change process, TG curve ask first derivative to obtain difference quotient thermogravimetric (DTG) curve temperature.Maximum weight loss rate pair on DTG curve
The decomposition temperature answered is Tmax。TmaxIt can reflect the thermal stability of test material.
The preparation of standard batten is completed using the 80 type injection molding machine of Victor of ENGEL company, Austria, injecting condition: material
Cylinder 180-190 DEG C of temperature, injection pressure 50MPa, injection speed 70mm/s, dwell pressure 40MPa, dwell time 25s, mold temperature
80 DEG C of degree.
Using vernier caliper measurement injection molding batten size to calculate flow direction molding shrinkage and vertical direction at
Type shrinking percentage.
Every test result is as shown in table 1:
The comparison of 1 embodiment characterization result of table
Flexible chain (t in table 11/2) reflection experimental temperature reciprocal under crystalline rate, t1/2It is smaller, illustrate crystallization speed
Rate is faster；In addition, peak crystallization temperature is higher, equally illustrate that crystalline rate is faster；Molding shrinkage (flow direction and Vertical Square
To) the smaller dimensional stability for illustrating sample is higher；Thermal decomposition temperature is higher, illustrates that the thermal stability of sample is higher.
Data in analytical table 1, it can be found that: compared with control experiment embodiment 9-12, the polyacetals of the auxiliary agent is added
The flexible chain of composition (embodiment 1-8) is shorter, and peak crystallization temperature is higher, and crystalline rate is accelerated.Comparing embodiment 1-8
And the molding shrinkage data of embodiment 9-12, it can be seen that the introducing of the auxiliary agent is conducive to polyacetal composition dimensionally stable
The raising of property.The thermal decomposition temperature of comparing embodiment 1-8 and embodiment 9-12 as it can be seen that the introducing of the auxiliary agent so that polyacetals
Thermal stability improves.In the range of the mass ratio of polyacetals and auxiliary agent is 1000:1~100:1, with the increasing of auxiliary agent ratio
Add, the crystalline rate of polyacetal composition is gradually accelerated, and dimensional stability and thermal stability also step up.In addition, comparison is real
Apply example 3 and embodiment 12, it will thus be seen that under polyacetals feed ratio identical with auxiliary agent, heretofore described auxiliary agent is to bunching
The promotion of the crystalline rates of aldehyde compositions, dimensional stability and thermal stability is more obvious.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of art technology
Member, under the premise of not departing from the method for the present invention, can also make several improvement and supplement, these are improved and supplement also should be regarded as
Protection scope of the present invention.
Claims (10)
1. a kind of polyacetal composition, which is characterized in that the composition includes polyacetals and auxiliary agent；The polyacetals and auxiliary agent
Mass ratio be 1000:1~100:1；Preferably, the mass ratio of the polyacetals and auxiliary agent is 300:1~800:1；
The auxiliary agent is copolymerized by cyclic ethers and/or cyclic acetal with isocyanate ester compound.
2. polyacetal composition according to claim 1, which is characterized in that the auxiliary agent is cyclic ethers and/or cyclic acetal
With the copolymer of isocyanate ester compound under the action of catalyst.
3. polyacetal composition according to claim 2, which is characterized in that the catalyst is lewis acid or non-volatile
Bronsted acid；Preferably, the catalyst be boron trifluoride etherate, boron trifluoride ether complex, heteropoly acid, with more
One or more of acid, heteropoly acid acid salt and isopolyacid acid salt.
4. polyacetal composition according to claim 2 or 3, which is characterized in that the cyclic ethers and/or cyclic acetal, different
The molar ratio of cyanate compound is 1000:1~10.
The molar ratio of the catalyst, cyclic ethers and/or cyclic acetal is 1~80ppm.
5. polyacetal composition according to claim 4, which is characterized in that the catalyst is dilute with nonactive organic solvent
It releases or dissolves, the organic solvent is in n-hexane, normal heptane, hexamethylene, formic acid, acetic acid, ethyl acetate, methyl formate
It is at least one.
6. polyacetal composition according to claim 5, which is characterized in that the cyclic ethers is one of following compound
Or it is several: ethylene oxide, propylene oxide, epoxy butane, 7-oxa-bicyclo[4.1.0, oxetanes, 1,3- dioxolane, 1,3,
5- trioxane；
The cyclic acetal is one or more of following compound: propylene glycol, diethylene glycol formal, three second two
Alcohol formal, 1,4- butylene glycol formal, 1,5- pentanediol formal, 1,6- butylene glycol formal.
7. polyacetal composition according to claim 6, which is characterized in that the isocyanate ester compound is aliphatic
Or aromatic polyisocyanate, preferably toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, hexa-methylene diisocyanate
Ester or its autopolymer, paraphenylene diisocyanate, 1,5- naphthalene diisocyanate, 3,3 '-dimethyl diphenyl diisocyanate, two hexamethylenes
Dicyclohexylmethane diisocyanate and one or more of isophorone diisocyanate or its autopolymer.
8. polyacetal composition according to claim 7, which is characterized in that the polyacetals is copolymerization acetal or equal bunching
The pellet or powder of aldehyde, melt flow rate (MFR) is 6~27g/10min pellet or powder preferably under 190 DEG C, 2.16kg loading condiction
Material.
9. a kind of preparation method of polyacetal composition as described in any one of claims 1 to 8, which is characterized in that the side
Method the following steps are included:
Cyclic ethers and/or cyclic acetal, isocyanate ester compound, catalyst are blended, auxiliary agent is prepared；
By polyacetals and auxiliary agent melting mixing, the polyacetal composition is prepared.
10. the preparation method of polyacetal composition according to claim 9, which is characterized in that the polyacetals and auxiliary agent
The temperature of melting mixing is 170~200 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910851099.9A CN110483943B (en) | 2019-09-10 | 2019-09-10 | Polyacetal composition and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910851099.9A CN110483943B (en) | 2019-09-10 | 2019-09-10 | Polyacetal composition and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110483943A true CN110483943A (en) | 2019-11-22 |
| CN110483943B CN110483943B (en) | 2022-04-22 |
Family
ID=68557069
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910851099.9A Active CN110483943B (en) | 2019-09-10 | 2019-09-10 | Polyacetal composition and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110483943B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112280238A (en) * | 2020-11-05 | 2021-01-29 | 青岛聚合利安工程技术有限公司 | Preparation method of enhanced high-thermal-stability polyacetal composition |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104072710A (en) * | 2013-03-28 | 2014-10-01 | 旭化成化学株式会社 | Manufacturing method of polyacetal copolymer |
| JP2015108132A (en) * | 2013-10-22 | 2015-06-11 | 旭化成ケミカルズ株式会社 | Method for producing polyacetal copolymer |
| CN109694543A (en) * | 2018-12-06 | 2019-04-30 | 万华化学集团股份有限公司 | A kind of polyacetal composition and preparation method thereof |
-
2019
- 2019-09-10 CN CN201910851099.9A patent/CN110483943B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104072710A (en) * | 2013-03-28 | 2014-10-01 | 旭化成化学株式会社 | Manufacturing method of polyacetal copolymer |
| JP2015108132A (en) * | 2013-10-22 | 2015-06-11 | 旭化成ケミカルズ株式会社 | Method for producing polyacetal copolymer |
| CN109694543A (en) * | 2018-12-06 | 2019-04-30 | 万华化学集团股份有限公司 | A kind of polyacetal composition and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112280238A (en) * | 2020-11-05 | 2021-01-29 | 青岛聚合利安工程技术有限公司 | Preparation method of enhanced high-thermal-stability polyacetal composition |
| CN112280238B (en) * | 2020-11-05 | 2022-07-19 | 青岛聚合利安工程技术有限公司 | Preparation method of enhanced high-thermal-stability polyacetal composition |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110483943B (en) | 2022-04-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100441686B1 (en) | Composition for polyoxymethylene composite resin and product formed therefrom | |
| EP1431428B1 (en) | Method for the production of polyoxymethylene fibers | |
| EP2505609B1 (en) | High impact resistant polyoxymethylene for extrusion blow molding | |
| EP3126446B1 (en) | Polyester composition | |
| US5344882A (en) | Polyacetal blends | |
| Vachon et al. | Compatibilization of PLA/PEBA blends via reactive extrusion: A comparison of different coupling agents | |
| EP0590420A1 (en) | Impact-resistant polyoxymethylene molding compositions | |
| CN110483943A (en) | A kind of polyacetal composition and preparation method thereof | |
| EP0757078A1 (en) | Impact-resistent thermoplastic moulding compositions | |
| US4181685A (en) | Thermoplastic molding compositions on the basis of polyoxymethylenes | |
| US4070415A (en) | Thermoplastic molding compositions on the basis of polyoxymethylenes | |
| CN113461930A (en) | Anhydride and epoxy macromolecule chain-extending tackifier and preparation method and application thereof | |
| EP0277630A1 (en) | Process for preparing moulding compositions having an enhanced cold impact resistance, based upon polyoxymethylenes and thermoplastic polyurethanes | |
| US3872182A (en) | Thermoplastic moulding composition on the basis of polyoxymethylene | |
| EP4077440A1 (en) | Thermoplastic moulding composition with good demoulding behaviour | |
| EP4121267A1 (en) | Method for producing a pet starting material that is suitable for use in an extrusion blow moulding method, and hollow article produced in the extrusion blow moulding method | |
| DE2233143B2 (en) | Thermoplastic molding compounds based on poly (oxymethylene) | |
| US4760119A (en) | Polyacetal compositions with improved hydrolytic stability | |
| CS216652B2 (en) | Thermoplastic forming substance | |
| KR101340025B1 (en) | Composition for plasticizer-free thermoplastic polyurethane elastomer and polyurethane elastomer having low hardness manufactured therefrom | |
| JPH0370766A (en) | Improved acetal polymer composition having high impact resistance | |
| KR20240154217A (en) | Resin composition including poly(glycolic acid) and film including the same | |
| JPH0375574B2 (en) | ||
| KR20240154218A (en) | Resin composition including poly(glycolic acid) and film including the same | |
| JP2024154373A (en) | Polyglycolic acid-containing resin composition and film containing same |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |