CN1135229A - Polyketone polymer compositions - Google Patents
Polyketone polymer compositions Download PDFInfo
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- CN1135229A CN1135229A CN 94194209 CN94194209A CN1135229A CN 1135229 A CN1135229 A CN 1135229A CN 94194209 CN94194209 CN 94194209 CN 94194209 A CN94194209 A CN 94194209A CN 1135229 A CN1135229 A CN 1135229A
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Abstract
Cross-linkable and cross-linked compositions comprising a major amount of polyketone polymer and a minor amount of an iodide salt. Compositions containing a iodide salt which is an onium iodide salt of nitrogen, phosphorus, arsenic, or a combination thereof of which the cation coordination sphere is shielded by aromatic substituents, or an alkali metal iodide, show improved oxidative stability. Further, the invention relates to a process for preparing such compositions and to a process for cross-linking such compositions.
Description
The present invention relates to polyketone polymer composition.
Polyketane polymers has many ideal physicalies, and this makes them be suitable for the application of engineering thermoplast.Especially, the linear alternately polyketane polymers of high molecular has performances such as high strength, rigidity, toughness, chemical resistant properties and wear resistant.Although these performances are suitable for many application, advantageously further improve some performance such as environmental stress crack resistance, chemical resistant properties, creep resistant, the use temperature of increase and the tensile strength of increase.A kind of line polymer chain that is used to provide these improved methods to relate to thermoplastic polymer known in the art crosslinked.Its example is a polyethylene, can be by the post-reactor crosslinked weather resistance that makes it to show increase, use temperature and intensity.
In order to keep flowing in good melt-processable and the parts manufacturing processed, be essentially the polymkeric substance of linear molecule structure before common hope use is crosslinked.Therefore, especially wish to have can be after the melt-processed crosslinked simple method that is essentially linear polymkeric substance.Common fusion manufacturing process is used in the high-crystallinity and the permission that make crosslinked polymer can keep last parts after the melt-processed, as injection moulding, extrusion molding and blow moulding.
The present invention relates to a kind of composition, it comprises relatively large polyketane polymers and more a spot of iodide salt, and condition is that said composition is not the composition of the sodium iodide (based on the metal content of polymkeric substance) that contains 5.0 parts per million.Have found that the said composition crosslinkable and had and show the composition of improved machinery and chemoresistance performance.In addition, the present invention relates to contain the blend of said composition.
The polyketane polymers that can be used for the present invention's practice has linear alternating structure and contains a carbon monoxide molecule basically for each ethylenically unsaturated hydrocarbons molecule.Preferred polyketane polymers is multipolymer or second ethylenically unsaturated hydrocarbons, particularly alpha-olefin of carbon monoxide, ethene and a kind of at least 3 carbon atoms such as the terpolymer of propylene of carbon monoxide and ethene.
When will this preferred polyketane polymers during, in this terpolymer, has the unit of 2 a part of ethene of combination at least for each unit in conjunction with a part of second hydrocarbon as the main polymeric constituent of blend of the present invention.Preferably, the unit in conjunction with a part of second hydrocarbon is 10-100.Therefore the polymer chain of this preferred polyketane polymers is represented by following repeating structure formula:
-[--CO--(--CH
2--CH
2--)-]
x--[CO--(-G)--]-
y
Wherein G is for being not more than 0.5 by the ethylenically unsaturated hydrocarbons part of at least 3 carbon atoms of ethylenic unsaturated bond polymeric and the ratio of y: x.When the multipolymer with carbon monoxide and ethene is used for the present composition, do not exist second hydrocarbon and this multipolymer to represent by following formula (wherein y is 0).When y is not 0, promptly use terpolymer, discovery-CO-(CH
2-CH
2-)-unit and-CO-(G-)-unit is random in whole polymer chain, and y: the ratio of x is preferably 0.01-0.1.As if the definite kind of end group is not remarkable to the influence of polymer performance, thereby this polymkeric substance can be represented with the structural formula with above-mentioned polymer chain.
Especially meaningfully number-average molecular weight is 1000-200,000 polyketane polymers, and particularly those number-average molecular weights (by gel permeation chromatography) are 20,000-90,000 polyketane polymers.The physicals of polymkeric substance will depend in part on molecular weight, and polymkeric substance is multipolymer or terpolymer, and the scale that depends on second hydrocarbon of existence under the terpolymer situation.The general fusing point of polymkeric substance is 175 ℃-300 ℃, more generally is 210 ℃-270 ℃.The intrinsic viscosity (LVN) of preferred this polymkeric substance is measured as 0.5dl/g-10dl/g with standard capillary device for measuring viscosity in meta-cresol under 60 ℃, more preferably 0.8dl/g-4dl/g.
The preferred method of producing polyketane polymers is already at EP-A-181014, EP-A-248483, and EP-A-600554 describes among EP-A-314309 and the EP-A-391579.
Useful iodide salt is to make crosslinked those of polyketane polymers under proper condition.The example of these salt comprises those of listing in table 1.
The linear polyketane polymers that contains capacity (on a small quantity) iodide salt can be by said composition is present under high temperature in the oxygen and is crosslinked.Although do not want to depend on any specific theory, it is believed that some oxidations can take place polyketane polymers, this oxidation is the catalytic crosslinking reaction in the presence of iodide salt.Crosslinked degree can be controlled by the amount that is exposed to heat and oxygen.The crosslinked horizontal required time of acquisition expection and employed temperature or available oxygen level are inversely proportional to.Effectively source of oxygen is an air.The heat that needs should be enough to cause the crosslinked of polymkeric substance.Needed heat can obtain under about 70 ℃ preferred operations temperature.Although the polyketane polymers that the inventive method can crosslinked fusing in the presence of capacity oxygen is preferred crosslinked under the temperature of the crystalline melt point that is lower than this polymkeric substance usually.
Be used to that the method for polyethylene crosslinking is comprised (1) uses high-energy radiation known in the art, (2) thermal chemical reaction and (3) moisture bring out (moisture induced) reaction.Method (1) and (2) are depended on or are produced free radical intermediate by radiation or by radical initiator such as organic superoxide.In polyethylene, these free radical intermediates cause the chemically crosslinked of polymkeric substance interchain; Yet these methods also are not suitable for all polyolefine polypropylene and polybutene is exactly that free radical causes and can not cause crosslinked example, and chain rupture takes place for their on the contrary.These methods also have the known shortcoming of some those of skill in the art.
Use moisture that the method for polyethylene crosslinking is at first required vinyl silanes unit free radical grafting to polyolefine, could produce chemically crosslinked with the water reaction then.Occur in after the melt-processed because of crosslinked, allow to use conventional manufacture method and after crosslinked, keep high-crystallinity so this method is the same with radiation curing.
Aforesaid method also not exclusively is applicable to polyketane polymers.Radiation curing is impossible, because in polyketone chain-breaking reaction may take place.Relate to apply enough heats so that substantially for linear polymkeric substance fusing when crosslinked takes place and flow into the thermochemical crosslinking method of expection form also inapplicable.At first, the processing temperature of polyketone is significantly higher than polyethylene, and this will cause the early stage decomposition of any radical initiator (organo-peroxide).Secondly, different with simple polyolefine is that the reactivity of polyketone is more varied and cause the free radical cracking of undesirable polymkeric substance to react.
If some method beyond the available free radical method is carried out the silane grafting, then the moisture of polyketane polymers is crosslinked is possible.According to expectation, if with replacing usually vinyl group used in polyethylene with the group of ketone reaction such as amine, then the silane grafting method of polyketone is that the example of feasible amine comprises (trialkylsilkl) alkylamine and (trialkylsilkl) arylamines.
The present invention adopts and a kind ofly can be dissolved in the line polymer among the HFIPA (hexafluoroisopropanol) fully and make it crosslinked so that it become only can be by this solvent-swollen.A kind of method that becomes known for measuring crosslinking degree is by measuring its solubleness or swelling capacity in appropriate solvent.Suitable solvent is the low polar solvent of molecular volume normally, and especially those have the solvent of strong hydrogen bonding characteristic.The example of this kind solvent comprises hexafluoroisopropanol, meta-cresol and phenol.Preferred hexafluoroisopropanol is because it can at room temperature dissolve polyketane polymers.
In addition, be surprisingly found out that already that the compositions table that contains some iodide salt revealed improved oxidative stability.
The shortcoming of the linear alternate polymer of carbon monoxide and at least a ethylenically unsaturated hydrocarbons is their deterioration in physical properties when thermooxidative degradation.This degraded is owing to the chemical erosion of atmosphericoxygen to polymer chain, and it is the feature of most of organic polymers (if not whole words).Oxidation generally is autocatalytic and the effect of Yin Re and oxygen and taking place, and therefore uses term " thermooxidative degradation ".Hope is stablized the variation that suppresses polymer performance by making polymkeric substance to the disadvantageous effect of heat and oxygen.Industrial have manyly be used for making thermoplastic polymer to the stable thermal oxidation stabilizer of this kind degraded.Yet, many known only effective to a certain extent or absolutely void when being used for polyketane polymers to effective thermo-stabilizer such as polyolefine, polymeric amide, polyacetal, polyacrylic ester.
Have now found that a kind of oxidation-stabilized polyketone polymer composition.Said composition comprises the iodide salt or the alkaline metal iodide of nitrogen, phosphorus, arsenic or its combination, wherein shielded by aromatic substituent in salt middle-jiao yang, function of the spleen and stomach ion coordination zone, condition is that said composition is not the composition that contains 5.0ppmw sodium iodide (based on the metal content of polymkeric substance).The melt stability of having described polymkeric substance in EP-A-600554 can be subjected to the disadvantageous effect of alkali (soil) metal-salt existence.In experiment 1, a kind of composition that contains 5/1000000ths weight part sodium iodides (based on the metal content of polymkeric substance) had been described already.
The present composition can prepare by polyketane polymers is contacted with iodide salt.More particularly, these methods can comprise a) by powder mixes or solvent deposition iodide salt with carry out melting mixing after polyketane polymers contacts, b) by iodide salt being diffused in the polymer product with this polymkeric substance of solution-treated that contains this iodide salt, the two has the solvent of certain compatibility preferred use and polymkeric substance and iodide salt, or c) use and be included in the blend polymer that applies capacity precursor of generation iodide salt when hot and produce iodide salt on the spot.Preferred iodide salt is introduced by diffusion.
The thermooxidative degradation of organic polymer is relevant because of the chemical reaction variation between polymkeric substance and the atmosphericoxygen with polymer performance.Although machinery (mechanistic) approach of oxidation can be different between oxidising process complexity and the different polymkeric substance, but oxidation is quickened by heat usually, usually caused by trace impurity such as metal ion or organic degradation auxiliary agent and general characteristic is autocatalytically, wherein carbon radicals and hydrogen peroxide free radical have constituted the main intermediate in this catalytic cycle.Polymkeric substance has fallen to increase this catalytic cycle with oxygen consumption and has produced the material of oxidation, these materials or constitute the part of polymkeric substance, or discharge with gaseous product.The material of these oxidations can further help the degraded of polymkeric substance.For example, hydroperoxide itself are also unstable and can resolve into new free radical, it or decompose or decompose by heat effect by trace impurity catalysis, new then free radical causes extra oxidation cycle.
For polyketone, it is believed that thermal oxidation method relates to the formation of oxide compound, this oxide compound makes the polymer chain cracking and causes the reduction of molecular weight and the loss that polymkeric substance tangles under aging condition.This finally causes the polymer machinery degradation, descends and embrittlement as shock strength reduction, extension at break.Therefore advantageously or by total oxidation speed that reduces polyketane polymers or the polymer chain breakdown rate that reduces them make them present stable to these degradation.
Useful especially iodide salt is listed in table 1 in the thermooxidizing stabilization.
Table 1
1 other alkali metal iodide salt such as lithium iodide, potassiumiodide and sodium iodide are also within the scope of the present invention.
The amount of iodide salt is as the criterion in the weight of polyketane polymers and is generally 0.0001-10%, more specifically is 0.001-10%, preferably is as the criterion with the weight of polyketane polymers and counts 0.1-1.0%.
In addition, if find not only to have iodide salt, but also have a hindered phenol, more precisely a kind of composition, then the thermal ageing performance of polymkeric substance is improved, wherein hindered phenol is a phenylpropionic acid 3,5-two (1, the 1-dimethyl ethyl)-4-hydroxyl stearyl and/or phenylpropionic acid 3,5-two (1, the 1-dimethyl ethyl)-4-hydroxyl-ethylene two (oxidation-2,1-ethylidene) ester.
After the preparation, already the polyketane polymers of stabilization to the mechanical property of expection as at high temperature and the retentivity of the brittle resistance when being exposed under the air conditions test be improved.At United States Patent (USP) U.S.4, disclosed this test is carried out aerobic thermal ageing with polymer samples under differing temps in 994,511, and the time of brittle rupture (fracture) takes place when bending rapidly with 180 ° of angles in monitoring.
Following embodiment and Biao further specify all respects of the present invention.
The embodiment of stabilization
The polymkeric substance that is used for following embodiment is described in table 2.In whole embodiment process, use thermal aging test to determine the performance of polymeric additive.In this test, preparing thickness by melt extrusion or compression moulding is 5.1 * 10
-4Or 7.6 * 10
-4The polymer sheet of m (20 or 30 mil).Then test sample is cut into the wide fillet of 1cm, and put into the forced air circulation furnace of 100 ℃ or 125 ℃.Regularly fillet is taken out and when cooling, is folded into 180 ° of angles from stove.When sample fully become fragile and in this testing sequence fracture the time think to destroy and record brittle time.
Table 2
The polyketane polymers that is used for illustrative embodiment
a5.1 * 10
-4The thick extrudate piece of m (20 mil)
bPercentage ratio based on polyketane polymers weight
cCalcium hydroxy apetite
d4,4 ', 4 "-((2,4,6-trimethylammonium-1,3,5-benzene three bases) three (methylene radical)) three (2,6-two (1, the 1-dimethyl ethyl) phenol)
eEthene and 2-methyl-2-polymerizing acrylic acid thing
| Polymkeric substance | ??LVN ??dl/g | ?Tm ?℃ | Form | Basic additive b |
| A | ??1.95 | ?220 | Extrudate piece a | ?0.5％Irganox?1330 d?0.5％Nucrel?535 e |
| B | ??1.86 | ?220 | Extrudate piece a | ?0.2％Irganox?1330 d?0.2％CaHAp c?0.3％Nucrel?535 e |
| C | ??1.77 | ?220 | Powder | ?0.2％Irganox?1330 d?0.2％CaHAp ?0.3％Nucrel?535 e |
| D | ??1.73 | ?220 | Powder | ?0.2％Irganox?1330 d?0.2％CaHAp ?0.3％Nucrel?535 e |
| E | ??1.87 | ?220 | Powder | Do not have |
Embodiment 1-5
The iodide additive was to the effect of heat aging when embodiment 1-5 explanation was mixed polyketane polymers with diffusion way.By with 5.1 * 10
-4The polymer A of m (20 mil) sheet form immerses in a kind of water composition under the 90-95 ℃ of temperature and to prepare test sample in 20-25 minute.Used water is the HPLC level, and it is the OmniSolv that EM Science provides.Water composition used in embodiment 2-5 comprises: water only, 0.30wt%ZnI
2, 2.0%KI and only can be dissolved in saturated Ph in the 90-95 ℃ of water on a small quantity
4PI.After exposing, the cooling polymer sample is cleaned any surface residues, and under 50 ℃ in vacuum drying oven with nitrogen purge dry night.Cut out 1 centimetre wide oven test bar then from the sheet that exposes.For being exposed to Ph
4The sample of PI carries out neutron activation test, to be determined at the iodide that exist in the polymkeric substance after this exposure.Measure residual iodine and be about 900ppm, calculate thus in this sample and have 0.33%Ph
4PI.Thermal aging test the results are shown in table 3.
Table 3
Mix iodide additive in the polyketane polymers with diffusion way
| Required fate takes place to destroy | |||
| Embodiment | Expose | ???125℃ | ??100℃ |
| ????1 | ?????- | ???20 | ??78 |
| ????2 | ???H 2O | ???22 | ??81 |
| ????3 | ???H 2O/ZnI 2 | ???21 | ??83 |
| ????4 | ???H 2O/KI | ???27 | ??121 |
| ????5 | ???H 2O/Ph 4PI | ???45 | ??234 |
Embodiment 2 and 3 shows and simply polymer sheet only is exposed to water or is exposed to ZnI
2Solution do not improve thermostability.Be exposed to KI and Ph
4PI causes the improvement of thermostability, and Ph
4PI stablizes the ability of this polyketane polymers and wants much superior, and it is greater than the twice of contrast-embodiment 1.
Embodiment 6-10
The test sample that is used for embodiment 6-10 prepares by diffusion way, uses polymer A then and contains the 2.0% corresponding water composition of testing additive and test by embodiment 2-5 is described.The results are summarized in table 4.
Table 4
Mix iodide salt additive in the polyketane polymers with diffusion way
| Required fate takes place to destroy | |||
| Embodiment | Expose | ????125℃ | ????100℃ |
| ????6 | ??????- | ????24 | ????108 |
| ????7 | ?H 2O/Ph 4PBr | ????21 | ????113 |
| ????8 | ?H 2O/Ph 4PCl | ????25 | ????110 |
| ????9 | ?H 2O/Et 4NI | ????26 | ????117 |
| ????10 | ?H 2O/Ph 4PI | ????44 | ????245 |
Embodiment 7,8 and 10 shows at Ph
4In the P halide salts, only iodide make polyketane polymers stable.Embodiment 9 shows alkyl ammonium iodide such as tetraethyl ammonium iodide (Et
4NI) can not effectively stablize polyketane polymers.This shows that not all iodide salt is all effective as the stablizer of polyketane polymers.
Embodiment 11-13
According to the described preparation embodiment of embodiment 1-5 11-13, the different extrudate pieces that are to use polymer B replace polymer A.Be similar to the test sample that embodiment 7-10 prepares embodiment 12 and 13.
Thermal ageing the results are shown in table 5.
Table 5
The comparison that adds the iodide salt in the polyketane polymers with diffusion way
| Required fate takes place to destroy | |||
| Embodiment | Expose | ????125℃ | ????100℃ |
| ???11 | ?????- | ????18 | ????97 |
| ???12 | ?H 2O/CaI 2 | ????19 | ????96 |
| ???13 | ?H 2O/Ph 4PI | ????28 | ????128 |
These embodiment show that again not all iodide salt all makes polyketane polymers stable.Calcium iodide was compared with contrast and do not demonstrate improvement on brittle time.
Embodiment 14-16
Embodiment 14-16 illustrates Ph
4The powder mixes of PI and polyketane polymers, then melt-processed causes the thermo-oxidative stability of polymer composition to be improved.Embodiment 15 and 16 passes through 100g polymkeric substance C powder and Ph
4The PI powder mixes, then by rotate one night homogenizing prepare.Extrude on the 15mmBakcr-Perkins twin screw extruder that then each mixture is to operate under about 250 ℃ of melt temperatures.Use the composition of extruding to prepare the sheet of 30 mil thick by compression moulding then.As shown in table 6, band Ph
4The composition of PI is compared the brittle time that shows obvious improvement under 125 ℃ with contrast.
Table 6
Be melt blended into the Ph in the polyketane polymers
4The aging resistance of PI
| Required fate takes place to destroy | ||
| Embodiment | Additive | ????125℃ |
| ???14 | ????????- | ????8 |
| ???15 | ????0.25％Ph 4PI | ????18 |
| ???16 | ????0.50％Ph 4PI | ????17 |
Embodiment 17-26
The composition of embodiment 17-26 is by preparing by the described melt-processed of carrying out of embodiment 14-16, and the different polymkeric substance D that are to use replace polymkeric substance C.The thermal aging test result who is shown in table 7 shows that the iodide salt (embodiment 18-22) of being with alkyl substituent does not have static stabilization to polyketane polymers.Embodiment 25 and 26 explanation Ph
4The static stabilization of the iodide salt beyond the PI, these iodide salts also contain the positively charged ion that is shielded by aromatic substituent, promptly contain two (triphenyl phosphoranediyl) ammonium salt and triazolium salt respectively.In these embodiments, some is little in the increase of stability, but its size is similar to Ph
4The effect that PI is brought in this polymkeric substance (embodiment 24).
Table 7
Be melt blended into the aging resistance of the iodide salt of polyketane polymers
aTwo (triphenyl phosphoranediyl) ammonium iodide
b5-methyl-3-(methylthio group)-1,4-phenylbenzene-1H-1,2,4-triazole iodide
| Required fate takes place to destroy | |||
| Embodiment | Additive | ????125℃ | ????100℃ |
| ???17 | ???????- | ????17 | ????73 |
| ???18 | ?0.43％Ph 3MePI | ????16 | ????48 |
| ???19 | ?0.49％(PhO) 3MePI | Can not process | |
| ???20 | ?0.28％Et 4NI | ????12 | ????30 |
| ???21 | ?0.50％Et 4NI | ????12 | ????32 |
| ???22 | ?0.22％Me 4NI | ????11 | ????30 |
| ???23 | ??????- | ????22 | |
| ???24 | ?0.3％Ph 4PI | ????26 | |
| ???25 | ?0.43％PPNI a | ????25 | |
| ???26 | ?0.25％TI b | ????27 | |
Embodiment 27-39
The composition of embodiment 27-39 prepares by carrying out melt-processed shown in the embodiment 14-16 by polymkeric substance shown in the use table 8 and additive.Embodiment 30 shows and only uses PPh
4I has improved brittle resistance.Embodiment 31 shows when the merchant being sold hindered phenol anti-oxidants such as Irganox 1076 and Ph in polyketane polymers
4PI has obtained significant improvement when mixing.This mixing causes with independent use any to compare the thermal ageing performance being improved.Embodiment 33-39 shows by phosphine and organic iodide component and forms phosphonium iodide on the spot as using Ph
4The same stability of improving polyketane polymers effectively of PI.Embodiment 34-37 shows independent use triphenylphosphine or 1, and the 4-diiodo-benzene there is no contribution to the stability of polyketane polymers.Yet the combination of these additives significantly improves the heat aging performance of resulting polymers among the embodiment 33.Embodiment 38 and 39 further shows the beneficial effect when mixing organic iodide and triphenylphosphine in the additive group.
Table 8
Be melt blended into the aging resistance of phosphonium iodide in the polyketane polymers and that produce on the spot
a3-(3,5-di-t-butyl-4-hydroxyphenyl) propionic acid Octadecane base ester
b3,5-two (1, the 1-dimethyl ethyl)-4-hydroxyl-ethylene two (oxidation-2,1-ethylidene) Phenpropionate
| Embodiment | Polymkeric substance | Additive | 125 ℃ of required fates take place to destroy |
| ?27 | ?E | Do not have | ????15 |
| ?28 | ?E | ?0.5％Irganox?1076 a | ????19 |
| ?29 | ?E | ?0.5％Irganox?245 b | ????26 |
| ?30 | ?E | ?0.3％Ph 4PI | ????38 |
| ?31 | ?E | ?0.5％Irganox1076 a，0.3％Ph 4PI | ????43 |
| ?32 | ?E | ?0.5％Irganox?245 b，0.3％Ph 4PI | ????36 |
| ?33 | ?E | ?0.2％PPh 3，0.3％PhI 2，0.5％ ?Irganox?245 b | ????42 |
| ?34 | ?E | ?0.3％PPI 2，0.5％Irganox?245 b | ????11 |
| ?35 | ?D | ?- | ????18 |
| ?36 | ?D | ?0.2％PPh 3 | ????13 |
| ?37 | ?D | ?0.3％PPH 3 | ????15 |
| ?38 | ?E | ?0.5％Irganox?245 b, 0.3%9-iodo phenanthrene | ????26 |
| ?39 | ?E | ?0.5％Irganox?245 b, 0.3%9-iodo phenanthrene, 0.2%PPh 3 | ????38 |
Crosslinked embodiment
Embodiment 1
It is polyketane polymers A and the 0.3wt% tetraphenyl phosphonium iodide (PPh of 1.87dl/g with intrinsic viscosity that fusing point is about 220 ℃
4I) and 0.5%Irganox1076 on 15mmBaker Perkins forcing machine, mix, this forcing machine is operated under about 250 ℃ melt temperature.Do not use any additives to press extruded polymer A as mentioned above, prepare contrast.Afterwards, under nitrogen, extrude ball, be compression molded into 5.1 * 10 then with the vacuum drying oven drying at 50 ℃
-4The thick sheet of m (20 mil).
From sheet, cut out test sample, use the Blue M that is set in 125 ℃ to force air oven to make it to be exposed to oxygen and pine for the wide fillet form of 1cm.From this baking oven, take out sample after exposing 11 days, and use hexafluoroisopropanol (HFIPA) to carry out gpc analysis as solvent.Gpc analysis uses placed in-line ZORBAX1000 and 60PSM chromatographic column and uses Waters 410 differential refractometers to make detector.
Table 1 shows that just as desired, two unexposed samples are dissolved among the HFIPA fully in linear polyketane polymers.After being exposed to heat and oxygen, it is solvable and show molecular weight and molecular weight not conform to the polyketane polymers of iodide additive.The polymer sample that contains iodide becomes swollen gel (50% colloidal sol), shows that it is a cross-linked polymer.Yet with embrittlement only just took place at the 15th day do not contain PPh
4The sample of I is compared, and this sample embrittlement occurs up to the 43rd talent in same baking oven.The PPh of table 2 polyketane polymers
4I promotes crosslinked
| ????PPh 4I content | 125 ℃ of fate @ | Molecular weight (Mn) |
| Do not have | ????0 | ????55900 |
| Do not have | ????11 | ????34510 |
| ????0.3％ | ????0 | ????55280 |
| ????0.3％ | ????11 | Insoluble |
Embodiment 2
Fusing point is about 220 ℃, and LVN is 1.95dl/g and contains 0.5%Irganox1330 and the polyketane polymers B of 0.5%Nucrel535 melt extrudes into 5.1 * 10
-4The sheet of m (20 mil).With 1 centimetre of width bar of this sheet by embodiment 1 described being exposed in heat and the oxygen.Except that these fillets, another group fillet is immersed 85 ℃ saturated PPh
4In the I aqueous solution 20 minutes.Take out these fillets, clean, dry in 50 ℃ of vacuum drying ovens under purging with nitrogen gas then.To contain PPh by diffusion then
4These fillets of I are by being exposed to as mentioned above in heat and the oxygen.Table 2 shows that the polyketane polymers that contains iodide becomes insoluble swell gel (20% colloidal sol) again in HFIPA after heat exposes, and the sample of not handling with iodide is solvable fully and demonstrate molecular weight and molecular weight.This embodiment shows can be after the parts manufacturing but add iodide before applying heat and oxygen, thereby obtains crosslinked polyketone.
Table 3
PPh
4I is to the DIFFUSION TREATMENT of polyketone parts
| ?PPh 4I handles | Tian Shuo @125 ℃ | Molecular weight (Mn) |
| Do not have | ????0 | ????50562 |
| Do not have | ????5 | ????34660 |
| Have | ????5 | Insoluble |
Embodiment 3
Contain the polymkeric substance fillet of potassiumiodide or tetraethyl ammonium iodide by embodiment 2 described preparations and test, different is to replace PPh with each iodide solution of 2wt%
4I solution.It is insoluble in HFIPA after following 10 days at 125 ℃ to observe two samples.This shows PPh
4Iodide beyond the I have also promoted the oxidative cure of polyketone.
Embodiment 4
It is that the polyketane polymers C of 1.84dl/g is injection molded into 1/8 inch ASTM D-638 tension force stick that fusing point is about 220 ℃ and LVN.Will part rod be exposed in heat and the oxygen 20 days, and another group was at first used 80 ℃ PPh before the heat exposure by embodiment 1 is described
4The I saturated aqueous solution was handled 90 minutes.Table 3 shows that heat exposes tensile property, GPC and the DSC result of front and back.GPC all measures on the top layer of tension force stick and core, and DSC measures on the top layer.This embodiment shows PPh
4I has promoted oxidation cross-linked, thereby bigger tensile strength and solvent resistance is provided, and keeps high-crystallinity simultaneously.
This embodiment shows PPh
4I has promoted oxidation cross-linked, thereby bigger tensile strength and solvent resistance is provided, and keeps high-crystallinity simultaneously.Crosslinked, as shown in insoluble among the HFIPA, only containing PPh
4I and being combined with fully is exposed in the sample of heat and oxygen and occurs, promptly only in the outer layer segment appearance of sample.Result as crosslinked contains PPh
4The sample of I increases by 24% on yield strength, and does not contain PPh
4The schedule of samples of I reveals oxidative degradation, thereby causes surrendering the decline (number-average molecular weight on top layer (Mn) descends 40%) with molecular weight.The crosslinked in this way degree of crystallinity that do not reduce with respect to no cross-linked polymer, this can find out from the big fusing calorific value that is directly proportional with degree of crystallinity.
Table 4
PPh
4I is to the DIFFUSION TREATMENT of polyketone parts
aRupture stress is 9180psi.
| ????PPh 4I handles | 125 ℃ of fate @ | Yield strength psi | Breaking strain % | Mn (top layer) | Mn (core) | ????Tm， ????℃ | Melting heat J/g |
| Do not have | ????0 | ????8700 | ????670 | ???46825 | ????222 | ???81 | |
| Do not have | ????20 | There is not surrender a | ????23 | ???28163 | ???52305 | ????222 | ???103 |
| Have | ????0 | ????8700 | ????670 | ???46825 | |||
| Have | ????20 | ????10790 | ????70 | Insoluble | ???53482 | ????219 | ???100 |
Claims (13)
1. composition, it contains relatively large polyketane polymers and more a spot of iodide salt, and condition is that said composition is not the composition of the sodium iodide (based on the metal content of polymkeric substance) that contains 5.0 parts per million.
2. according to the composition of claim 1, wherein polyketane polymers is linear alternately polyketane polymers.
3. according to the composition of claim 1 and/or 2, wherein iodide salt is the iodide salt or the alkaline metal iodide of nitrogen, phosphorus, arsenic or its combination, and wherein salt middle-jiao yang, function of the spleen and stomach ion coordination zone is shielded by aromatic substituent.
4. according to the composition of claim 3, wherein iodide salt is selected from tetraphenylphosphoniphenolate, 5-methyl-3-(methylthio group)-1,4-phenylbenzene-1H-1,2,4-triazole, two (triphenyl phosphoranediyl) ammonium, 4-iodine substituted phenyl triphenyl phosphonium, 1,4-two (triphenyl phosphonium) benzene and 9-phenanthryl triphenyl phosphonium.
5. according to the composition of claim 4, wherein iodide salt is the tetraphenyl phosphonium iodide.
6. according to each composition among the claim 3-5, said composition further comprises a kind of hindered phenol.
7. according to the composition of claim 6, wherein this hindered phenol is a phenylpropionic acid 3, and 5-two (1, the 1-dimethyl ethyl)-and 4-hydroxyl stearyl and/or phenylpropionic acid 3,5-two (1, the 1-dimethyl ethyl)-4-hydroxyl-1,2-ethylene (oxidation-2,1-ethylidene) ester.
8. according to each composition among the claim 1-7, wherein the amount of iodide salt is 0.0001-10wt%.
9. according to each composition among the claim 1-8, said composition is crosslinked.
10. prepare a kind of method for compositions, this method comprises allows polyketane polymers contact with iodide salt, and condition is that this iodide salt is not a sodium iodide.
11. preparation is according to a kind of method for compositions of claim 9, this method comprises the solution-treated polyketane polymers with iodid-containing salt.
12. crosslinked as each described method for compositions among the claim 1-8, this method comprises at high temperature is present in the oxygen said composition.
13. comprise blend according to each a kind of composition among the claim 1-9.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US08/155,395 US5407982A (en) | 1993-11-19 | 1993-11-19 | Process for producing stabilized polyketone polymers and polymers produced therefrom |
| US08/155,396 US5486581A (en) | 1993-11-19 | 1993-11-19 | Crosslinked polyketone polymer |
| US155,396 | 1993-11-19 | ||
| US155,395 | 1993-11-19 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1135229A true CN1135229A (en) | 1996-11-06 |
| CN1041425C CN1041425C (en) | 1998-12-30 |
Family
ID=26852292
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94194209A Expired - Fee Related CN1041425C (en) | 1993-11-19 | 1994-11-17 | Polyketone polymer compositions |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0729488A1 (en) |
| JP (1) | JPH09505106A (en) |
| CN (1) | CN1041425C (en) |
| AU (1) | AU683515B2 (en) |
| CA (1) | CA2176937A1 (en) |
| WO (1) | WO1995014056A1 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9663499B2 (en) | 2013-06-07 | 2017-05-30 | The California Institute For Biomedical Research | Small molecule inhibitors of fibrosis |
| US10336735B2 (en) | 2014-12-10 | 2019-07-02 | The Scripps Research Institute | Small molecule inhibitors of fibrosis |
| CN111205625A (en) * | 2020-04-20 | 2020-05-29 | 胜利油田东润机械工程有限责任公司 | Aliphatic polyketone lining pipe and preparation method thereof |
| CN111205624A (en) * | 2020-04-20 | 2020-05-29 | 胜利油田东润机械工程有限责任公司 | Aliphatic polyketone fully-coated sucker rod and preparation method thereof |
| CN111763273A (en) * | 2019-04-02 | 2020-10-13 | 北京诺维新材科技有限公司 | Iodine complex and preparation method and application thereof |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5955019A (en) * | 1997-10-06 | 1999-09-21 | Shell Oil Company | Solution spinning polyketone fibers |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5388857A (en) * | 1977-01-17 | 1978-08-04 | Teijin Ltd | Heat stable polyamide composition |
| US5010264A (en) * | 1988-09-09 | 1991-04-23 | Mabuchi Motor Co., Ltd. | Miniature motor having positive-coefficient thermistor |
| US5122591A (en) * | 1990-03-22 | 1992-06-16 | Shell Oil Company | Polymerization of co/olefin with increased catalyst composition concentration during polymerization start up |
| EP0600554B1 (en) * | 1992-11-30 | 1999-02-03 | Shell Internationale Researchmaatschappij B.V. | Preparation of copolymers of carbon monoxide with ethylenically unsaturated compounds, composition and method for melt processing |
-
1994
- 1994-11-17 CN CN94194209A patent/CN1041425C/en not_active Expired - Fee Related
- 1994-11-17 AU AU10663/95A patent/AU683515B2/en not_active Ceased
- 1994-11-17 JP JP7514232A patent/JPH09505106A/en active Pending
- 1994-11-17 WO PCT/EP1994/003851 patent/WO1995014056A1/en not_active Application Discontinuation
- 1994-11-17 EP EP95901408A patent/EP0729488A1/en not_active Withdrawn
- 1994-11-17 CA CA 2176937 patent/CA2176937A1/en not_active Abandoned
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9663499B2 (en) | 2013-06-07 | 2017-05-30 | The California Institute For Biomedical Research | Small molecule inhibitors of fibrosis |
| US9981956B2 (en) | 2013-06-07 | 2018-05-29 | The Scripps Research Institute | Small molecule inhibitors of fibrosis |
| US10336735B2 (en) | 2014-12-10 | 2019-07-02 | The Scripps Research Institute | Small molecule inhibitors of fibrosis |
| CN111763273A (en) * | 2019-04-02 | 2020-10-13 | 北京诺维新材科技有限公司 | Iodine complex and preparation method and application thereof |
| CN111205625A (en) * | 2020-04-20 | 2020-05-29 | 胜利油田东润机械工程有限责任公司 | Aliphatic polyketone lining pipe and preparation method thereof |
| CN111205624A (en) * | 2020-04-20 | 2020-05-29 | 胜利油田东润机械工程有限责任公司 | Aliphatic polyketone fully-coated sucker rod and preparation method thereof |
| CN111205624B (en) * | 2020-04-20 | 2020-07-31 | 胜利油田东润机械工程有限责任公司 | Aliphatic polyketone fully-coated sucker rod and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| AU1066395A (en) | 1995-06-06 |
| AU683515B2 (en) | 1997-11-13 |
| CA2176937A1 (en) | 1995-05-26 |
| JPH09505106A (en) | 1997-05-20 |
| WO1995014056A1 (en) | 1995-05-26 |
| EP0729488A1 (en) | 1996-09-04 |
| CN1041425C (en) | 1998-12-30 |
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