CN107254171A - A kind of sulfone polymer composition and its application - Google Patents
A kind of sulfone polymer composition and its application Download PDFInfo
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- CN107254171A CN107254171A CN201710453376.1A CN201710453376A CN107254171A CN 107254171 A CN107254171 A CN 107254171A CN 201710453376 A CN201710453376 A CN 201710453376A CN 107254171 A CN107254171 A CN 107254171A
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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
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
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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
- C08K5/13—Phenols; Phenolates
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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
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
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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
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
- C08K5/3477—Six-membered rings
- C08K5/3492—Triazines
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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
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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Abstract
The invention discloses a kind of sulfone polymer composition and its application.The sulfone polymer composition includes：One kind, phosphorous acid ester additive agent and the phenol additives that are obstructed in polysulfones, polyether sulfone, PPSU；The phosphorous acid ester additive agent and phenol additives heat resistance thermogravimetic analysis (TGA) (TGA) sign of being obstructed, 360 DEG C of weight loss are not higher than 10%.Wherein, the phenol additives that are obstructed account for phosphorous acid ester additive agent and are obstructed the 1~50% of phenol additives quality summation.Sulfone polymer composition prepared by the present invention can be applied in food security, household electrical appliance, health care, electronic apparatus, Aero-Space or derived energy chemical field.
Description
Technical field
The present invention relates to technical field of polymer materials, and in particular to a kind of sulfone polymer composition and the heat being made from it
Plastic moulding composition and application.
Background technology
Sulfone polymer belongs to special high temperature-resistant transparent thermoplastic engineering plastics, mainly includes polysulfones PSU, polyether sulfone PES and poly-
Phenylene sulfone PPSU three types.Its excellent in mechanical performance, rigidity is big, wear-resisting, high intensity, and heat endurance is high, with higher
Glass transition temperature, about 190 DEG C.Even if excellent mechanical property is also kept at high temperature, it is 160 that temperature, which is used for a long time,
DEG C, 190 DEG C of short-period used temperature, and hydrolysis, good stability of the dimension, molding shrinkage is small, nontoxic, radiation hardness, resistance to combustion, have from
The property put out, there is excellent electrical property, chemical stability within the scope of broad temperature, is resistant to general acid, alkali, salt.Therefore, for a long time with
Come in electronic apparatus, machining, automobile, medical apparatus, food processing and the field such as stickness paint is not widely used.It is special
In terms of not being food contact and health care, the requirement more and more higher to material, one of which most prominent requirement is exactly conduct
Visual form, needs sulfone polymer light color, transparent, pure to be as good as color dot, such as glasses, coffee machine form, baby's children's feeding bottle etc..
Since sulfone polymer is developed from last century the seventies, its production technology turns into known technology, ready to use solution
Polymerization produces high polymer by electrophilic substitution reaction, and used solvent is generally high boiling protic, such as ring
Fourth sulfone or 1-METHYLPYRROLIDONE, monomer used include two halobenzene sulfones and dihydroxy phenol or benzene sulfone, with alkali metal or alkali metal
Compound is salt forming agent, hydroxyl first is converted into phenates base, then be condensed with halide end group.The polymer solution of production passed through
Polymer powder or fine particle are obtained after filtering, crush, purify and drying.Preferably pass through double screw extruder or Single screw extrusion
Machine carries out melt pelletization, obtains slightly yellow transparent resin particle.In fact, sulfone polymer is the high polymer very sensitive to heat,
Being easy to crosslink the pollutant effects such as degraded or external environment dust after it is heated causes nigrescence color, and transparency declines,
Bubble, or the appearance property for having heterochromatic points of contamination change, and when melting shear-mixed in an extruder, this phenomenon is even more serious,
Also it is difficult to maintain original appearance luster even if using most gentle melt Treatment technique for processing and processing environment, therefore,
Person skilled is directed to exploitation, and that necessary additive is added during synthesis or melting extrusion is pure to obtain uniform color
Net naval stores.
With the extensive use of transparent sulfone polymer, the exploitation of the sulfone polymer of transparent and stable is increasingly by technical staff
Attention, there is patent GB1398133A to disclose early in 1975 and phosphorous acid ester additive agent added in sulfone polymer to increase
The heat resistance of polymer and the report of transparency, to before and after 2003, disclose patent such as US2003011501 again,
What US2003011502 and WO2004058870 was announced has the yellowing of reduction and the polyether sulphone composition of high light transmittance properties,
Including PSU, PES and PPSU, the antioxidant of addition only has this type of phosphite ester, a small amount of dyestuff is also added in addition and glimmering
Optical brightener.Patent disclosed above and the proof that studies for a long period of time of the present inventor, phosphite ester have really to suppressing xanthochromia
The effect of benefit, but fisheye and the variation issue of bubble are not referred to.Inventor is by the discovery that studies for a long period of time, and phosphite ester is due to existing
Facile hydrolysis, heatproof is not high enough and the problems such as poor compatibility with resin matrix, not only the transparency to resin has adverse effect,
The appearance of patent disclosure is extremely difficult to, and the bad result such as obvious fisheye and bubble is finally produced during addition increase.
It is generally believed that the generation of fisheye is because high polymer main chain there occurs branched or crosslinking chemical reaction, or some are small different
Thing is mixed into so that index of refraction changes and produce difference in appearance；Bubble is the volatilization because small molecule, and these small molecules can
Can the compound such as the relatively low additive of heat resistance decompose and produce.In addition, sulfone polymer is more sensitive to additive, addition
Agent species is excessive or during excessive addition product easily deform, distort, pressure embrittlement the problems such as, reduce the use longevity of product
Life.
The content of the invention
The purpose of the present invention is to overcome the shortcomings of that prior art is present there is provided a kind of sulfone polymer composition, can effectively be kept away
Exempt to produce fisheye and bubble, while the problem of solving oxidation stain.
The above-mentioned purpose of the present invention is achieved by the following technical programs：
A kind of sulfone polymer composition, it is composed of the following components：
One kind in polysulfones, polyether sulfone, PPSU；
Phosphorous acid ester additive agent；
Be obstructed phenol additives；
The heat resistance of the phosphorous acid ester additive agent and the phenol additives that are obstructed is characterized with thermogravimetic analysis (TGA) (TGA), 360 DEG C
Weight loss be not higher than 10%；The phenol additives that are wherein obstructed account for phosphorous acid ester additive agent and are obstructed the 1 of phenol additives quality summation
~50%.
The selection of additive will disclosure satisfy that rotten degraded will not occur under higher processing temperature for sulfone polymer, and sulfone is poly-
About 360 DEG C of the processing temperature of compound, therefore additive should have good heat-resisting quantity.The high phosphorous of present invention selection temperature classification
Acid esters additive, while compounding the phenol additives that are obstructed of addition good heat stability, additive is not easily decomposed to solve during high temperature
Certainly produce air bubble problem.Improve material frequently by addition hindered phenol anti-oxidants in general-purpose plastics and engineering plastics field
The color inhibition and ageing-resistant effect of material.In sulfone polymer, hydrogen bond and ehter bond on phenyl ring easily by oxygen radical attack and then
Cause molecule chain branching, degraded, the mechanism of action of hindered phenol antioxygen is that phenolic hydroxyl group easily provides proton and catches free radical and loses it
It is living；The mechanism of action of phosphite ester is that hydroperoxide decomposition terminates peroxy radical and alkoxy free group again simultaneously.Inventor
It was found that both additives are added in sulfone polymer can produce synergy, the synergy refers to hindered phenol as main anti-
Oxygen agent and phosphite ester are as auxiliary antioxidant, and the former captures peroxy radical, suppress polymer molecule chain branching, degraded, resistance
Only fisheye is produced, and also cuts off polymer oxidative degradation chain reaction；The latter then has redox characteristic, on the one hand can decompose
The torpescence products such as the hydroperoxides generation alcohol ketone in polymer, on the other hand can reduce oxidized phenolic antioxidant,
And itself generates colourless or white phosphate compounds after being oxidized, the color and luster change of high polymer can be suppressed to greatest extent,
Improve the color stability of product.Therefore, hindered phenol and phosphite ester occur cooperative effect and make resisting etiolation effect more obvious.
Study and find through inventor, phenol additives quality of being obstructed accounts for phosphorous acid ester additive agent and phenol additives quality of being obstructed is total
Sum 1~50% when the preferable synergy of competence exertion.When one side sulfone polymer is by thermal oxide, the phenyl ring at its ehter bond ortho position
H can more generate hydroperoxides, on the other hand the easy formation quinones substance if Hinered phenols additive level is too high
Make the aobvious green of sulfone polymer, thus hindered phenol additive level it is appropriate when can then effectively act as the effect of anti-oxidant discoloration,
It can also avoid producing fisheye and bubble simultaneously, obtain uniform color, pure transparent naval stores.
Preferably, the phenol additives that are obstructed account for phosphorous acid ester additive agent and be obstructed phenol additives quality summation 10~
30%.
The phosphorous acid ester additive agent and hindered phenol additive level that the sulfone polymer composition is included account for sulfone polymerization
Compositions are calculated by weight to 100ppm~5000ppm.
The polysulfones, polyether sulfone, PPSU are following structure:
Wherein structural formula I is polysulfones PSU, and formula II is polyether sulfone PES, and formula II I is PPSU PPSU, its
Middle n is 10~500.
The phosphorous acid ester additive agent is the aromatic series phosphite ester that monoalkyl and/or dialkyl group replace.
Preferably, the phosphorous acid ester additive agent is four (2,4- di-tert-butyl-phenyl) [1,1 '-diphenyl] -4,4 '-two
One or both of double (2,4- di-tert-butyl-phenyls) pentaerythritol esters of phosphite ester, diphosphorous acid.
The phenol additives that are obstructed for four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol esters, 1,3,
5- tri- (the 4- tert-butyl group -3- hydroxyl -2,6- dimethyl benzyls) -1,3,5- triazines -2,4,6- (1H, 3H, 5H)-triketone, 4,6- tri-
One or more in (3,5- di-tert-butyl-4-hydroxyl benzyls) benzene.
The fisheye or Air Bubble Size are measured according to ASTM3351-93 methods, and sample is molded index, chi with injection machine
Very little is 200*200*0.5mm.
The sulfone polymer composition is processed into various products using general moulding process, including injection molding, is compression molded into
One or more in type, blow molding, extrusion molding.
The sulfone polymer composition can carry out blending and modifying, and the blending and modifying is included in dyeing, filling, fiber reinforcement
One or more；The dyeing is to be dyed using organic and/or inorganic toner；The filling is filled out using inorganic matter
Fill；The fiber reinforcement carries out fiber reinforcement using glass fibre and/or carbon fiber.
The sulfone polymer composition is in food security, household electrical appliance, health care, electronic apparatus, Aero-Space or energy
Application in the chemical field of source.
Compared with prior art, the present invention has the advantages that：
In the prior art, additive phosphite ester has beneficial effect to suppressing sulfone polymer product xanthochromia, but does not carry
And fisheye and the variation issue of bubble.Inventor is by the discovery that studies for a long period of time, and phosphite ester is due to having facile hydrolysis, high temperature resistant not
Enough the problem of, not only the transparency to resin is adversely affected, it is difficult to reach the appearance of patent disclosure, and addition
Obvious fisheye and bubble are produced during amount increase.The high phosphorous acid ester additive agent of present invention selection temperature classification, while compounding addition
The phenol additives that are obstructed of good heat stability, by adjusting the proportioning of two kinds of additives, are both avoided that generation fisheye and bubble, together
When can effectively act as the effect of anti-oxidant discoloration.
Embodiment
The present invention is further expalined explanation with reference to specific embodiment, it describes more specific and detailed, but
Therefore the limitation to the scope of the claims of the present invention can not be interpreted as, as long as being obtained using the form of equivalent substitution or equivalent transformation
The technical scheme obtained, all should be included within the protection domain of the claims in the present invention.
Following examples and comparative example it is raw materials used be purchased in market.
Thermal weight loss carries out TGA tests using Germany Netzsch company's T G 209F3 types thermogravimetric analyzer, and test condition is：
N2Atmosphere, 500 DEG C are warming up to 20 DEG C/min speed.Table 1 lists this two classes additive thermal weight loss data：
The thermal weight loss of the additive of table 1
| Phosphite ester model | PEPQ | 608 | S-9228 | 618 |
| 360 DEG C of weightlessness (%) | 9.2 | 6.3 | 7.9 | 43.6 |
| Hindered phenol model | 1790 | 1330 | 1010 | |
| 360 DEG C of weightlessness (%) | 9.5 | 6.8 | 9.9 |
PEPQ：Four (2,4- di-tert-butyl-phenyls) [1,1 '-diphenyl] -4,4 '-diphosphites；
618：Diphosphorous acid two (octadecyl) pentaerythritol ester；
608：Double (2,4- di-tert-butyl-phenyls) pentaerythritol esters of diphosphorous acid；
S-9228：Double (2,4- di-tert-butyl-phenyls) pentaerythritol esters of diphosphorous acid；
608 is identical with S-9228 main component, and difference is that S-9228 contains hundreds of isopropanols of ppm grades of hydrolysis-resisting agent three
Amine.
1790：1,3,5- tri- (the 4- tert-butyl group -3- hydroxyl -2,6- dimethyl benzyls) -1,3,5- triazines -2,4,6- (1H,
3H, 5H)-triketone；
1330：4,6- tri- (3,5- di-tert-butyl-4-hydroxyl benzyls) benzene；
1010：Four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol esters.
In following examples and comparative example, extruder used is D25mm type Berstorff double screw extruders, about 300
Mixture extrusion is carried out under~350 DEG C of melting temperatures, additive is added in extruder after being first pre-mixed uniformly in toner
Melting extrusion, extruder feeding capacity is 35kg/h, and screw speed about 250rpm, extrusion temperature is as shown in table 2.
The extruder melting extrusion temperature of table 2
| Machine barrel | Machine barrel 1 | Machine barrel 2 | Machine barrel 3 | Machine barrel 4 | Machine barrel 5 | Machine barrel 6 | Machine barrel 7 | Machine barrel 8 | Head |
| Temperature DEG C | 200 | 280 | 300 | 330 | 300 | 300 | 320 | 330 | 340 |
Color board is prepared using 50 tons of KraussMaffei injection machines, colour table thickness 0.5mm, and size is 200mm*200mm.
Melt overheat is avoided using as far as possible gentle technique or shears too strong caused discoloration, about 300~360 DEG C of melting temperature, back pressure
About 5MPa and screw speed 50rpm, total cycle time are not higher than 30s.Blend used is dried at 150 DEG C after molding
4h.Injection machine technique is as shown in table 3.
The injection machine technique of table 3
| Injection temperature | Nozzle, DEG C | Rear portion, DEG C | Middle part, DEG C | Front portion, DEG C |
| 340 | 330 | 320 | 320 | |
| Position | Three sections | Two sections | One section | / |
| Injection pressure | 125bar | 120bar | 120bar | / |
| Dwell pressure | / | 50bar | 50bar | / |
| Dwell time | 8s | Cool time | 12s | / |
| Mould temperature | 180℃ | Screw speed | 200rpm | / |
Performance test methods：
Fisheye or bubble：Using Canadian SUNPLUS companies produce SP-Y-1700-B types flake determine projecting apparatus according to
ASTM 3351-93 methods carry out sample test, amplify 8 times, contrast standard hole records fisheye size, respectively record >=0.8mm,
0.4~0.8mm, 0.2~0.4mm, ＜ 0.2mm number.
Fisheye is distinguished with bubble：If flake is more regular circle and sharpness of border is considered as bubble, otherwise recognized
To be fisheye.
Light transmittance, mist degree：Light transmittance/mist degree the analyzer produced with Shanghai Shen Guang instrument plants, exists according to ASTM D-1003
Thickness is detection on 2mm injection colour table.
Lab values：With U.S.'s Color I 7000A type color difference meters, the method according to as defined in CIE is made with white standard colour table
Tested for background, L values represent whiteness or brightness, higher explanation is whiter, and a values are red on the occasion of expression, negative values greenness, b
Value is on the occasion of expression yellow, negative values blueness.
Embodiment 1
5.586kg is sequentially added in equipped with thermometer, logical nitrogen tube, condensation water knockout drum, the 50L polymeric kettles of agitator
The 4 of (30mol), 4 '-dihydroxybiphenyl, the 4 of 8.787kg (30.6mol), 4 '-dichloro diphenyl sulfone, the ring for adding 32.62kg
Fourth sulfone, is stirred and to be warming up to 100 DEG C of dissolving monomers transparent to solution, adds 3.396kg (32.039mol) salt forming agents Na2CO3With
132.6g (0.961mol) salt forming agents K2CO3, 2L dimethylbenzene is subsequently added, continuation is warming up to salt-forming reaction under stirring and started, system
The azeotropic mixture that the water of middle generation is generated with dimethylbenzene goes out into condenser pipe condensation by protection air-blowing and drips to layering in water knockout drum, on
The dimethylbenzene of layer is back in system again；Scope of the temperature at 200 DEG C~210 DEG C is maintained, when collecting water close to theoretical value
When (540g), backflow 20 minutes is further continued for, not observing has the globule to fall, it was demonstrated that, redistillation simultaneously releases dimethylbenzene into salt completely,
230 DEG C of beginning polymerisations are gradually heating to, viscosity is now detected and starts increase, constant temperature is after 2.5 hours, Viscosity Growth Curve
Slope is substantially zeroed, illustrates that system viscosity is completely constant, terminates reaction；Stop stirring and heat, material be poured slowly into without from
White strip solid is cooled in sub- water, then is broken into pulverizer powdered, is boiled 1 hour with deionized water, crosses elimination water
Point, so it is repeated 10 times, until filtrate is not become cloudy with silver nitrate detection, illustrates that by-product salt removes clean, filtering in powder
Afterwards polymer with 120 DEG C of dryings of vacuum drying oven to constant weight, produce PPSU PPSU.Additive PEPQ and 1790 are used 2:
1 weight mixes 10 minutes to ensure to be well mixed, then squeezed with single screw rod than adding in PPSU toners with homogenizer
Go out machine and carry out melt pelletization, obtain sulfone polymer composition plastic particles, wherein additive total content accounts for sulfone polymer composition
It is calculated by weight to 5000ppm.Again colour table is prepared with injection machine melting.Carried out with prepared transparent color plate fisheye and bubble with
And the index test of xanthochromia performance, as a result as shown in table 4~6.
Embodiment 2
Preparation process condition be the same as Example 1 prepares PPSU PPSU, and additive PEPQ and 1330 are used into 1:1 weight
Than adding in PPSU toners, mix 10 minutes to ensure to be well mixed with homogenizer, then with single screw extrusion machine entered
Row melt pelletization, obtains sulfone polymer composition plastic particles, and wherein additive total content accounts for sulfone polymer composition by weight
It is calculated as 3000ppm.Again colour table is prepared with injection machine melting.Fisheye and bubble and xanthochromia are carried out with prepared transparent color plate
The index test of performance, as a result as shown in table 4~6.
Embodiment 3
Preparation process condition be the same as Example 1 prepares PPSU PPSU, and additive PEPQ and 1010 are used into 99:1 weight
Measure than adding in PPSU toners, mix 10 minutes to ensure to be well mixed with homogenizer, then use single screw extrusion machine
Melt pelletization is carried out, sulfone polymer composition plastic particles are obtained, wherein additive total content accounts for sulfone polymer composition by weight
Amount is calculated as 500ppm.Again colour table is prepared with injection machine melting.Fisheye and bubble and Huang are carried out with prepared transparent color plate
Become the index test of performance, as a result as shown in table 4~6.
Embodiment 4
Preparation process condition be the same as Example 1, by starting monomer 4,4 '-dihydroxydiphenylsulisomer is replaced by 6.849kg (30mol)
2,2 '-bis- (4- hydroxy phenyls) propane (BPA), prepare polysulfones PSU.Additive 608 and 1330 is used 2:1 weight ratio
Add in PSU toners, mix 10 minutes to ensure to be well mixed with homogenizer, then melted with single screw extrusion machine
Melt granulation, obtain sulfone polymer composition plastic particles, wherein additive total content accounts for sulfone polymer composition and calculated by weight
For 100ppm.Again colour table is prepared with injection machine melting.Fisheye and bubble and xanthochromia performance are carried out with prepared transparent color plate
Index test, as a result as shown in table 4~6.
Embodiment 5
Preparation process condition be the same as Example 1, by starting monomer 4,4 '-dihydroxydiphenylsulisomer is replaced by 7.508kg (30mol)
4,4 '-dihydroxydiphenylsulisomer, the resin of preparation is polyether sulfone PES.Additive S-9228 and 1790 are used 4:1 weight ratio adds
Enter in PES toners, mix 10 minutes to ensure to be well mixed with homogenizer, then melted with single screw extrusion machine
Granulation, obtains sulfone polymer composition plastic particles, wherein additive total content accounts for sulfone polymer composition and is calculated by weight to
4000ppm.Again colour table is prepared with injection machine melting.Fisheye and bubble and xanthochromia performance are carried out with prepared transparent color plate
Index test, as a result as shown in table 4~6.
Embodiment 6
Preparation process condition be the same as Example 5 prepares polyether sulfone PES, and additive S-9228 and 1330 are used into 3:1 weight
Than adding in PES toners, mix 10 minutes to ensure to be well mixed with homogenizer, then carried out with single screw extrusion machine
Melt pelletization, obtains sulfone polymer composition plastic particles, and wherein additive total content accounts for sulfone polymer composition by weight
Calculate as 2000ppm.Again colour table is prepared with injection machine melting.Fisheye and bubble and xanthochromia are carried out with prepared transparent color plate
The index test of energy, test result is as shown in table 4~6.
Embodiment 7
Preparation process condition be the same as Example 1 prepares PPSU PPSU, and additive PEPQ and 1330 are used into 7:3 weight
Than adding in PPSU toners, mix 10 minutes to ensure to be well mixed with homogenizer, then with single screw extrusion machine entered
Row melt pelletization, obtains sulfone polymer composition plastic particles, and wherein additive total content accounts for sulfone polymer composition by weight
It is calculated as 3000ppm.Again colour table is prepared with injection machine melting.Fisheye and bubble and xanthochromia are carried out with prepared transparent color plate
The index test of performance, as a result as shown in table 4~6.
Embodiment 8
Preparation process condition be the same as Example 1 prepares PPSU PPSU, and additive PEPQ and 1330 are used into 9:1 weight
Than adding in PPSU toners, mix 10 minutes to ensure to be well mixed with homogenizer, then with single screw extrusion machine entered
Row melt pelletization, obtains sulfone polymer composition plastic particles, and wherein additive total content accounts for sulfone polymer composition by weight
It is calculated as 3000ppm.Again colour table is prepared with injection machine melting.Fisheye and bubble and xanthochromia are carried out with prepared transparent color plate
The index test of performance, as a result as shown in table 4 and 5.
Embodiment 9
Preparation process condition be the same as Example 1 prepares PPSU PPSU, and additive PEPQ and 1330 are used into 99:1 weight
Measure than adding in PPSU toners, mix 10 minutes to ensure to be well mixed with homogenizer, then use single screw extrusion machine
Melt pelletization is carried out, sulfone polymer composition plastic particles are obtained, wherein additive total content accounts for sulfone polymer composition by weight
Amount is calculated as 3000ppm.Again colour table is prepared with injection machine melting.Fisheye and bubble and Huang are carried out with prepared transparent color plate
Become the index test of performance, as a result as shown in table 4~6.
Embodiment 10
Preparation process condition be the same as Example 1 prepares PPSU PPSU, and additive PEPQ and 1330 are used into 1:1 weight
Than adding in PPSU toners, mix 10 minutes to ensure to be well mixed with homogenizer, then with single screw extrusion machine entered
Row melt pelletization, obtains sulfone polymer composition plastic particles, and wherein additive total content accounts for sulfone polymer composition by weight
It is calculated as 5000ppm.Again colour table is prepared with injection machine melting.Fisheye and bubble and xanthochromia are carried out with prepared transparent color plate
The index test of performance, as a result as shown in table 4~6.
Embodiment 11
Preparation process condition be the same as Example 1 prepares PPSU PPSU, and additive PEPQ and 1330 are used into 1:1 weight
Than adding in PPSU toners, mix 10 minutes to ensure to be well mixed with homogenizer, then with single screw extrusion machine entered
Row melt pelletization, obtains sulfone polymer composition plastic particles, and wherein additive total content accounts for sulfone polymer composition by weight
It is calculated as 100ppm.Again colour table is prepared with injection machine melting.Fisheye and bubble and xanthochromia are carried out with prepared transparent color plate
The index test of performance, as a result as shown in table 4~6.
Comparative example 1
Preparation process condition be the same as Example 2 prepares not doping during PPSU resins, extruding pelletization.Performance test
It is shown in Table shown in 4~6.
Comparative example 2
Preparation process condition be the same as Example 2 prepares PPSU resins, by phosphite ester 618, the i.e. (octadecane of diphosphorous acid two
Base) pentaerythritol ester added in PPSU toners, with homogenizer mix 10 minutes it is well mixed to ensure, then use single spiral shell
Bar extruder carries out melt pelletization, obtains sulfone polymer composition plastic particles, wherein additive total content accounts for sulfone polymer group
Compound is calculated by weight to 3000ppm.Again colour table is prepared with injection machine melting.It is gentle that fisheye is carried out with prepared transparent color plate
The index test of bubble and xanthochromia performance, test result is as shown in table 4~6.
Comparative example 3
Preparation process condition be the same as Example 2 prepares PPSU resins, and additive 1330 is added in PPSU toners,.
Mix 10 minutes to ensure to be well mixed with homogenizer, then melt pelletization is carried out with single screw extrusion machine, obtain sulfone polymerization
Compositions plastic particles, wherein additive total content account for sulfone polymer composition and are calculated by weight to 3000ppm.Again with injection
Machine melting prepares colour table.The index test of fisheye and bubble and xanthochromia performance is carried out with prepared transparent color plate, as a result such as
Shown in table 4~6.
Comparative example 4
Preparation process condition be the same as Example 2 prepares PPSU resins, and additive PEPQ is added in PPSU toners, uses
Homogenizer mixes 10 minutes to ensure to be well mixed, then carries out melt pelletization with single screw extrusion machine, obtains sulfone polymer
Composition plastic particles, wherein additive total content account for sulfone polymer composition and are calculated by weight to 3000ppm.Injection machine is used again
Melting prepares colour table.The index test of fisheye and bubble and xanthochromia performance is carried out with prepared transparent color plate, as a result such as table 4
Shown in~6.
Comparative example 5
Preparation process condition be the same as Example 2 prepares PPSU resins, and additive PEPQ and 1330 are used into 5:6 weight ratio adds
Enter in PPSU toners, mix 10 minutes to ensure to be well mixed with homogenizer, then melted with single screw extrusion machine
Melt granulation, obtain sulfone polymer composition plastic particles, wherein additive total content accounts for sulfone polymer composition and calculated by weight
For 3000ppm.Again colour table is prepared with injection machine melting.Fisheye and bubble and xanthochromia performance are carried out with prepared transparent color plate
Index test, as a result as shown in table 4~6.
Comparative example 6
Preparation process condition be the same as Example 2 prepares PPSU resins, and additive PEPQ and 1330 are used into 3:5 weight ratio adds
Enter in PPSU toners, mix 10 minutes to ensure to be well mixed with homogenizer, then melted with single screw extrusion machine
Melt granulation, obtain sulfone polymer composition plastic particles, wherein additive total content accounts for sulfone polymer composition and calculated by weight
For 3000ppm.Again colour table is prepared with injection machine melting.Fisheye and bubble and xanthochromia performance are carried out with prepared transparent color plate
Index test, as a result as shown in table 4~6.
Comparative example 7
Preparation process condition be the same as Example 2 prepares PPSU resins, and additive 618 and 1330 is used into 1:1 weight ratio adds
Enter in PPSU toners, mix 10 minutes to ensure to be well mixed with homogenizer, then melted with single screw extrusion machine
Melt granulation, obtain sulfone polymer composition plastic particles, wherein additive total content accounts for sulfone polymer composition and calculated by weight
For 3000ppm.Again colour table is prepared with injection machine melting.Fisheye and bubble and xanthochromia performance are carried out with prepared transparent color plate
Index test, as a result as shown in table 4~6.
The fisheye of table 4 tests summary table
The bubble of table 5 tests summary table
The transparent test of table 6
Show that embodiment is substantially reduced compared to comparative example, fisheye and bubble from the performance test in table 4, table 5, table 6,
And the performance of anti-oxidant discoloration also increases.
Claims (10)
1. a kind of sulfone polymer composition, it is characterised in that composed of the following components：
One kind in polysulfones, polyether sulfone, PPSU；
Phosphorous acid ester additive agent；
Be obstructed phenol additives；
The heat resistance of the phosphorous acid ester additive agent and the phenol additives that are obstructed is characterized with thermogravimetic analysis (TGA) (TGA), 360 DEG C of mistake
Weight is not higher than 10%；The phenol additives that are wherein obstructed account for phosphorous acid ester additive agent and be obstructed phenol additives quality summation 1~
50%.
2. sulfone polymer composition according to claim 1, it is characterised in that the phenol additives that are obstructed account for phosphite ester and added
Plus agent and it is obstructed the 10~30% of phenol additives quality summation.
3. sulfone polymer composition according to claim 1, it is characterised in that the phosphorous that the sulfone polymer composition is included
Acid esters additive and hindered phenol additive level account for sulfone polymer composition and are calculated by weight to 100ppm~5000ppm.
4. sulfone polymer composition according to claim 1, it is characterised in that the polysulfones, polyether sulfone, PPSU knot
Structure formula is as follows：
Wherein structural formula I is polysulfones PSU, and formula II is polyether sulfone PES, and formula II I is PPSU PPSU；Wherein n
For 10~500.
5. sulfone polymer composition according to claim 1, it is characterised in that the phosphorous acid ester additive agent is monoalkyl
And/or the aromatic series phosphite ester of dialkyl group substitution.
6. sulfone polymer composition according to claim 5, it is characterised in that the phosphorous acid ester additive agent is four (2,4-
Di-tert-butyl-phenyl) [1,1 '-diphenyl] -4,4 '-diphosphites, double (2,4- di-tert-butyl-phenyls) Ji Wusi of diphosphorous acid
One or both of alcohol ester.
7. sulfone polymer composition according to claim 1, it is characterised in that the phenol additives that are obstructed is four [β-(3,5-
Di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, 1,3,5- tri- (the 4- tert-butyl group -3- hydroxyl -2,6- dimethyl benzyls) -
1,3,5- triazines -2,4,6- (1H, 3H, 5H)-triketone, one kind in 4,6- tri- (3,5- di-tert-butyl-4-hydroxyl benzyls) benzene or
It is a variety of.
8. sulfone polymer composition according to claim 1, it is characterised in that the sulfone polymer composition using it is general into
Type technique is processed into the one or more in product, including injection molding, compression molding, blow molding, extrusion molding.
9. sulfone polymer composition according to claim 1, it is characterised in that the sulfone polymer composition can be blended
Modified, the blending and modifying includes the one or more in dyeing, filling, fiber reinforcement；The dyeing uses organic and/or nothing
Machine toner is dyed；The filling is filled using inorganic matter；The fiber reinforcement uses glass fibre and/or carbon fiber
Carry out fiber reinforcement.
10. sulfone polymer composition described in any claim is defended in food security, household electrical appliance, medical treatment in claim 1~9
Application in life, electronic apparatus, Aero-Space or derived energy chemical field.
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| PCT/CN2018/089117 WO2018228201A1 (en) | 2017-06-15 | 2018-05-31 | Sulfone polymer composition and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018228201A1 (en) * | 2017-06-15 | 2018-12-20 | 金发科技股份有限公司 | Sulfone polymer composition and application thereof |
| CN111100349A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Chlorine-resistant composite, polyethylene composition, and preparation method and application thereof |
| CN111100348A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Polyolefin composition and preparation method and application thereof |
| CN114196206A (en) * | 2021-12-29 | 2022-03-18 | 苏州建发塑料制品有限公司 | PPSU high-temperature-resistant squirrel cage and preparation method thereof |
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| CN1729244A (en) * | 2002-12-17 | 2006-02-01 | 索维高级聚合物股份有限公司 | 4,4'-biphenol polysulfone compositions, process to prepare them, and articles made thereof |
| CN101608067A (en) * | 2009-07-06 | 2009-12-23 | 惠州市沃特新材料有限公司 | A kind of conductive engineering plastics and preparation method thereof |
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| KR100996377B1 (en) * | 2002-04-15 | 2010-11-24 | 솔베이 어드밴스트 폴리머스 엘.엘.씨. | Polysulfone compositions exhibiting very low color and high light transmittance properties and articles made therefrom |
| KR101593752B1 (en) * | 2013-10-01 | 2016-02-12 | 제일모직주식회사 | Thermoplastic resin composition with condictivity |
| CN107075254B (en) * | 2014-09-03 | 2020-02-28 | 索尔维特殊聚合物美国有限责任公司 | Sulfone polymer composition |
| CN107254171A (en) * | 2017-06-15 | 2017-10-17 | 金发科技股份有限公司 | A kind of sulfone polymer composition and its application |
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| CN1729244A (en) * | 2002-12-17 | 2006-02-01 | 索维高级聚合物股份有限公司 | 4,4'-biphenol polysulfone compositions, process to prepare them, and articles made thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018228201A1 (en) * | 2017-06-15 | 2018-12-20 | 金发科技股份有限公司 | Sulfone polymer composition and application thereof |
| CN111100349A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Chlorine-resistant composite, polyethylene composition, and preparation method and application thereof |
| CN111100348A (en) * | 2018-10-25 | 2020-05-05 | 中国石油化工股份有限公司 | Polyolefin composition and preparation method and application thereof |
| CN111100349B (en) * | 2018-10-25 | 2022-12-09 | 中国石油化工股份有限公司 | Chlorine-resistant composite, polyethylene composition, and preparation method and application thereof |
| CN111100348B (en) * | 2018-10-25 | 2022-12-09 | 中国石油化工股份有限公司 | Polyolefin composition and preparation method and application thereof |
| CN114196206A (en) * | 2021-12-29 | 2022-03-18 | 苏州建发塑料制品有限公司 | PPSU high-temperature-resistant squirrel cage and preparation method thereof |
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