WO2002042340A1 - Substances fonctionnelles derivees d'oligo-olefines presentant des groupes fonctionnels d'extremites - Google Patents
Substances fonctionnelles derivees d'oligo-olefines presentant des groupes fonctionnels d'extremites Download PDFInfo
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Definitions
- the present invention relates to novel functional substances, and more particularly, to various functions containing, as segments, oligoolefin chains derived from oligoolefins having terminal vinylidene double bonds obtained by highly controlled pyrolysis of polyolefins. New substances exhibiting properties. Background art
- the present inventors have disclosed in Japanese Patent Application Laid-Open No. 55-084302 a method for producing an ⁇ ⁇ ⁇ -gen-oligomer by thermal decomposition of a polymer material including poly ( ⁇ -olefin).
- Macromolecules, 28, 7973 (1995) and others have reported that highly controlled pyrolysis of polyolefins can yield monodisperse oligoolefins having vinylidene double bonds at both ends or one end.
- 1-butene is obtained as a by-product during the production of isoptylene and butadiene, but its polymer, poly (1-butene), has different properties from polyisobutylene, polybutadiene, and polypropylene, which has one less carbon unit in monomer units. Therefore, its use is limited and the production volume is extremely small.
- functional groups such as double bonds, hydroxyl groups, carboxyl groups, etc.
- waste polymers such as polymer pellets, which have become an environmental problem, can be used as the target polymer for highly controlled pyrolysis.
- amphiphiles also have hydrophilic further.
- Carbon dioxide (C0 2) is an essential substance for life with water.
- C0 2 gas discharged with the vast consumption of the carbon resources has been discussed at international conferences with regard to its emission control from Rukoto has become a cause of global warming.
- C0 2 emission gas to win regulations is the C0 2 generated by the combustion of carbon fuels recovered, there is an urgent need to be reused.
- the terminal vinylidene double bond of highly controlled pyrolysis products of polymers It is very difficult to extend the oligoolefin chain by directly polymerizing the chains.
- the present inventors have proposed the synthesis of a block copolymer of an oligopropylene having a butyl group at both ends synthesized by a polymer reaction and a polydimethylsiloxane having a hydroxy group at both ends in J. Polymer Science, 34, 36525 (1996). Reported to. However, additional testing is needed on this block copolymer to prove it is a block copolymer.
- Macromolecules, 12, 848, 853 (1979) reported that dimerization and dissociation of anthracene or pyrimidine bases such as peracyl and thymine reversibly occur by selecting the wavelength of irradiation light. I have.
- An object of the present invention is to provide novel functional substances containing, as segments, oligoolifin chains of oligo'refin obtained by highly controlled pyrolysis of polyolefins, and a method for producing them.
- the above functional substances are functional substances exhibiting amphiphilicity having a perfluoroalkyl group at the terminal of the oligoolefin chain, and photopolymerizable functional substances comprising telechelic oligomers containing photopolymerization / dissociation reversible groups.
- a light and Z or heat dissociating functional substance consisting of the polymer, a hydrolyzable oligoolefin / "oligorefin 'block copolymer, and an oligoolefin chain and polydimethylsiloxane chain And polymaleimides containing
- Another object is to provide an oligo (1-butene) having a terminal bilidene double bond. Disclosure of the invention
- the present invention is obtained by highly controlled pyrolysis of polyolefins.
- R represents an alkyl group having 1 to 3 carbon atoms, a phenyl group, a methylnoethyl mixed group or a methylhydrogen mixed group, and n is an integer of 2 to 100).
- R 1 represents ⁇ -R 2 —CH. Or R 3 —CH. Represents one, and R 2 represents 10 ° or
- R 1 3 is H-, Rf 1 - (CH 2 ) r - or a poly (Okishiarukiren) group
- R 1 ' represents H— or CH 3 —
- Rf 1 and Rf 2 each independently represent a perfluoroalkyl-containing group having 1 to 20 carbon atoms
- r is 0 or 1
- p is 2 p
- R 21 is R 22 — (C (0) 0) q — or R 23 — (where R 23 is hydrogen, a hydroxy group, Represents an alkyl group or an alkenyl group from to 8), wherein q is 0 or 1, and R 22 is selected from an anthranyl group when q is 1, a pyrimidyl group, a peracyl group or a thymidyl group when q is 0 Represents a photofunctional group that can be dimerized by exposure to actinic rays having a long wavelength of 30 Onm or more.
- a functional substance exhibiting light and / or thermal dissociation properties comprising a polymer obtained by photopolymerizing two or more molecules of the contained telechelic oligoolefin;
- R 31 represents an alkyl group or a phenyl group having 1 to 3 carbon atoms, which may be the same as or different from jR, and m represents 1 An integer of up to 100, which may be the same as or different from n
- a hydrolyzable functional substance comprising a multiblock copolymer of oligoolefin chains having a repeating unit of:
- c is an integer of 1 to 10 and h is an integer of 1 to 100
- Another aspect of the present invention is a pyrolysis product of poly (1-butene),
- FIG. 1 Pyrolysis product of poly (1-butene) obtained in Example 1-1 (oligo (1-butene) having a terminal bi-lidene group) and terminal male synthesized in Example 3-1 Oligo spectrum (1-butene).
- FIG. 2 1 H-NMR spectrum of a pyrolysis product of poly (1-butene) (oligo (1-butene) having a terminal vinylidene group) obtained in Example 11-11.
- Example 1-3 C-NMR scan Bae Kutonore in FIG pyrolysis products of poly obtained in Example 1-1 (1 Puten) (oligo having a terminal vinylidene down group (1-butene)).
- Fig. 4 Average number of vinylidene terminal groups (f ⁇ vs. thermal decomposition time curve) of the thermal decomposition product of poly (1-butene) (oligo (1-butene) having terminal vinylidene group) obtained in Example 1-1 .
- Example 11 Number average molecular weight (Mn) and degree of dispersion of molecular weight distribution of poly (1-butene) pyrolysis product (oligo (1-butene) having terminal viuridene group) obtained in Example 1-1 (Mw / Mn) vs. pyrolysis time curve.
- FIG. 7 TG curve of the pyrolysis product (oligo (1 butene) having a terminal viuridine group) of the poly (1 butene) obtained in Example 1-1.
- Fig. 8 Pyrolysis product of poly (1-butene) obtained in Example 1-1 (terminal viride Vs. thermal decomposition time curve of oligo (1-butene) having an amino group.
- Figure 1 1 of one embodiment IPP-synthesized in 2-1 0H Oyopi synthesized in Example 4- 1 iPP- DRF8 3 C- NMR spectra.
- Example IPP-3- 2 was synthesized in the A and Example 4-2 was synthesized in the IPP-TCRF8 of 1 3 C-NMR spectrum.
- Figure 14 1 H-NMR spectrum of iPP-TCRF8 synthesized in Example 4-2.
- Fig. 16 Surface tension no-copolymer concentration curve of SD-PE0 sample obtained in Example 4-4.
- Fig. 17 Curve of average micelle particle size / copolymer concentration of SD-PE0 sample obtained in Example 4-4.
- Chain line polypropylene containing hydroxy groups at both ends (iPP-OH),
- Dotted line polypropylene containing both ends butyl group (iPPv :).
- Fig. 22 Surface tension of dilute aqueous solution of triploch-co-integrated (iPP-b-PE0) solution obtained in Example 4-16.
- Fig. 23 The particle size distribution of the dispersion of the triplock copolymer (iPP-b-PE0) in the aqueous medium measured in Examples 4-6.
- Fig. 25 Surface tension of the sample measured in Example 4-6 Z copolymer concentration curve.
- Fig. 26 Ifi-NMR spectra of the telechelic propylene oligomer synthesized in Example 47 and the propylene oligomer having a hydroxy group at both ends used for the synthesis.
- FIG. 28 GPC curve of the reaction mixture obtained in Example 4-8.
- FIG. 34 Example 4 GPC curve of iPP-PDMS obtained in Example 10
- the present invention provides the following general formula (1)
- R represents an alkyl group having 1 to 3 carbon atoms, a phenyl group, a methyl Zethyl mixed group or a methyl / hydrogen mixed group, and n is an integer of 2 to 100).
- Oligoolefins having a vinylidene double bond at both ends or one end are used as starting materials. I do. ,
- the oligoolefins may be aliphatic polyolefins such as polypropylene, poly (1-butene), poly (1-ten), propylene / ethylene copolymer, propylene-1-butene copolymer, or aromatic polyolefins such as polystyrene.
- R in general formula (1) obtained by highly controlled pyrolysis is a methyl group, an ethyl group, a propyl group, a methyl / hydrogen mixed group, a methyl / ethyl mixed group or a phenyl derived from each of the above raw material polymers.
- oligoolefin a biuredene group at both ends or one end of an oligoolefin chain in which the repeating number ⁇ of one monomer is an integer of 2 to 100.
- This oligoolefin has a small degree of molecular weight distribution (Mw / Mn) and maintains the stereoregularity of the starting polymer very well.
- the oligoolefin having a terminal biylidene group is prepared by subjecting the starting polyolefin to a temperature of 300 to 450 ° C., preferably 350 to 400 ° C., under aeration of an inert gas such as nitrogen or argon. , For 30 to 240 minutes, preferably 40 to 180 minutes, by pyrolysis while removing volatile components.
- the present invention provides a compound represented by the following general formula (la) wherein R is an ethyl group in the above-mentioned general formula (1) which is a novel substance.
- Oligo (1-butene) having a bi-lidene group at both terminals And an oligo (1-butene) containing a terminal buriden group (1PB-VD), including an oligo (1-butene) having a bilidene group at one end.
- the terminal Biyuriden groups containing oligo (1-butene) (1PB- VD) is a thermal decomposition product obtained poly (1 Puten) and advanced control thermal decomposition at the conditions, 1 3 C one shown in FIG. 3 nuclear magnetic resonance (NMR) spectrum average terminal vinylidene groups (f TVD value) per one molecule calculated based on torque is the 1.5 3 to 1.7 5, having Biyuriden groups at both ends 1PB- It consists of a mixture of VD and 1PB-VD having a vinylidene group at one end.
- the 1PB-VD has a number average molecular weight (Mn) of 100 to 500 by gel permeation chromatography (GPC) shown in FIG. 5 and a degree of dispersion (Mw ZMn) of the molecular weight distribution. It is 2.5 or less, which maintains the tacticity of poly (1-butene) before thermal decomposition extremely well.
- the average number of terminal vinylidene groups (f TVD value) per molecule of the pyrolysis product is as follows: Oligo (1-butene) having vinylidene groups at both ends and Oligo (1-butene) having vinylidene groups at one end.
- the thermal decomposition temperature of the raw material poly (1-butene) is constant, it varies between 1.53 and 1.75 with the lapse of the thermal decomposition time.
- the number-average molecular weight (Mn) of the pyrolysis product is 100 to 500, preferably 100 to 250, and the degree of dispersion (Mw / Mn) of the molecular weight distribution is 2.5 or less, Preferably it is 2.0 or less.
- Mn and Mw / Mn decrease rapidly with the lapse of pyrolysis time, and eventually converge to almost constant values, Mn to about 1000 and MnZMw to about 1.8.
- the pyrolysis products do not show a distinct glass transition point (T g).
- the oligo (1-butene) having a vinylidene group at the terminal of the present invention is an oligopropylene having a vinylidene group at a terminal (iPP-VD) which is a highly controlled thermal decomposition product of polypropylene and a vinylidene terminal which is a highly controlled thermal decomposition product of polystyrene.
- iPP-VD oligopropylene having a vinylidene group at a terminal
- S-VD group-containing oligostyrene
- the functional substances of the present invention include an oligoolefin having a terminal biylidene group, and a functional group introduced by modifying the biylidene double bond of the oligoolefin, as shown in the following general formula (2):
- R 1 represents H—
- R 2 represents 1H Or 0
- R 3 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an arylke group), and an oligomer having a 10H group or an acid anhydride group at both ends or one end of an oligoolefin chain.
- Refin is used as a direct raw material for synthesis.
- the oligoolefin represented by the above general formula (2) is obtained by adding the terminal biylidene group-containing oligoolefin represented by the above general formula (1) to a THF solvent, adding BH 3 'THF-THF to form a terminal vinylidene group with hydroborane. And then oxidized by adding sodium hydroxide and aqueous hydrogen peroxide to modify the terminal bi-lidene double bond to a 10H group.
- Oligoolefin having a maleic acid anhydride group at both terminals or one terminal of the oligoolefin chain represented by the formula:
- the first functional substance of the present invention is an oligoolefin represented by the general formula (2).
- the following general formula (3) in which at least one perfluoroalkyl group is introduced at both ends or one end of an oligoolefin chain by using a terminal functional group via a poly (oxyalkylene) chain or not.
- R 13 represents H—, Rf 1- (CH 2 ) r — or a poly (oxyalkylene) group
- R 14 represents H— or CH 3 —
- Rf 1 and Rf 2 Each independently represents a perfluoroalkyl group having 1 to 20 carbon atoms, r is 0 or 1, p is 2 p (total of left and right), Zn is 0.1 to: L 0 ).
- This functional material has a water-repellent and supercritical C0 2 affinity segment consists of oleophilic segments and Per Furuoroarukiru group R f 1 or Rf 2 consisting Origoorefuin chain preferably further poly (Okishiarukiren ) Since it has a hydrophilic segment consisting of a chain, it exhibits amphipathicity and can be suitably used as a surfactant in various reactions using supercritical CO 2 as a solvent.
- a perfluoroalkyl group at both or one end of the oligoolefin chain represented by
- R in the formula is an alkyl group having 1 to 3 carbon atoms, that is, a methyl group from polypropylene, and a poly (1-butene) Represents a propyl group from poly (1-pentene) or a phenyl group from polystyrene.
- n represents the number of repetitions of the monomer unit, usually 2 or 1 to: L00, preferably an integer of 10 to 50, and can be appropriately selected depending on R and the required lipophilicity.
- R 11 is as defined in the general formula (3), and r is 0 or 1, preferably 0.
- Rf 1 is a perfluoroal having a linear or branched chain having 1 to 20, preferably 3 to 10 carbon atoms represented by the formula: F a + 1 C a — (where a is an integer of 1 to 20) a Kinore group, such as by the required water repellency and supercritical C0 2 affinity, carbon atoms Can be appropriately selected.
- a perfluoroalkyl group Rf 1 is added to both ends of an oligoolefin chain in which R 11 is Rf 1 — (CH 2 ) r —C (0) 0—CH 2 —. And a functional substance having a perfluoroalkyl group Rf 1 at one end where R 11 is H—, CH 3 — or H 0 —CH 2 —.
- the poly (oxyalkylene) group is a poly (oxyalkylene) in which one —OH group is blocked with an alkyl group, a perfluoroalkyl group, or the like, for example, poly (oxyethylene), poly (oxyethylene), Propylene).
- the poly (oxyalkylene) group is a hydrophilic group, and the length of the oxyalkylene chain can be appropriately selected depending on the required hydrophilicity and the like.
- the functional substance represented by the general formula (3a) includes an oligoolefin having a 10H group at a terminal of the oligoolefin chain represented by the general formula (2a);
- the functional substance represented by the general formula (3b) is a maleated oligoolefin having a terminal acid anhydride group represented by the general formula (2b);
- the functional substance represented by the general formula (2a) is characterized in that R is a phenyl group, and the oligostyrene having a 10H group at one end and an oligo (or poly) (oxyalkylene) are an ether bond.
- R is a phenyl group
- the oligostyrene having a 10H group at one end and an oligo (or poly) (oxyalkylene) are an ether bond.
- it is a BA block copolymer having a structure in which the terminal hydroxyl group is converted to a perfluorocarboxylic acid ester.
- n of the styrene monomer unit is not particularly limited, and depends only on the oligostyrene having a one-terminal bilidene group obtained as a raw material. Usually n is in the range of 2-10.
- Oligostyrene may be substituted in the molecule with various substituents. For example, those in which the benzene ring is substituted with an alkyl group, an alkoxy group, halogen, or the like, and those in which the ⁇ -position of the styrene chain is substituted with an alkyl, alkoxy group, or the like, are mentioned.
- the perfluoroalkyl group Rf 2 may be any of linear perfluoroalkyl and branched perfluoroalkyl having 1 to 20 carbon atoms, preferably 3 to 10 carbon atoms.
- the oligo (or poly) (oxyalkylene) chain is an oligo (or poly) (oxyethylene) wherein R 14 is 1H or an oligo (or poly) (oxypropylene) wherein R 14 is 1 CH 3 . And preferably oligo (or poly) (oxyethylene).
- the number of repetitions p of the oxyalkylene unit is also not particularly limited, and depends on the amount of the alkylene oxide used for the ring-opening polymerization for forming the oligo (or poly) (oxyalkylene) chain. Usually, p ranges from 1 to 50.
- the functional substance included in the general formula (3c) includes an oligostyrene having a 10H group at one end represented by the general formula (2a), an alkylene oxide, for example, ethylene.
- the compound can be produced by ring-opening polymerization of oxoxide, propylene oxide or the like in the presence of a catalyst, and further adding a perfluoroalkyl carboxylic acid to esterify the terminal 10H group. Ring-opening polymerization conditions such as the reaction amount of alkylene oxide, selection of catalyst system, reaction time, and temperature are described in, for example, The Society of Polymer Science, New Polymer Experiments. the synthesis of molecules "9 95 years, reference may be made to the Kyoritsu Shuppan).
- R gar CH 3 alone, perforations at both ends via a poly (Okishiarukiren) chains across the Origoorefuin chain is an CHsZ- H mixed group or a CH 3 Z ⁇ C 2 H 5 mixed base It is a BAB type block copolymer having a structure having a fluoroalkyl group.
- the repeating number n of the monomer unit of the oligoolefin chain is an integer of 15 to 100, and can be changed within the above range depending on the purpose of use, the type of the organic medium, and the like.
- R 14 is —H or one CH 3 , that is, a poly (oxyethylene) or poly (oxypropylene) chain, and the number of repeating p of the oxyalkylene unit is 2 p (total of right and left) as Zn 0.1 to: Within the range of L0.
- the amphiphilicity of the functional substance included in the general formula (3) is characterized by its ability to reduce surface tension and ability to form molecular aggregates.
- the surface tension of an aqueous dispersion of a functional substance can be measured, and its concentration dependence can be measured.
- the critical micelle concentration hereinafter referred to as “CMC”
- the average particle size of micelles in an aqueous dispersion of a functional substance can be measured, and its concentration dependence can be measured. By such a measurement, it can be confirmed that the functional substance forms a molecular assembly having a specific size.
- the functional substance included in the general formula (3) shows amphipathic property, it is hydrophilic. It can be used as a lipophilic surfactant, dispersant, emulsifier, surface modifier for polymer materials, etc. In addition, because of its unique ability to form molecular assemblies, it can be applied to new functional materials.
- At least one end of the oligoolefin chain has a photopolymerization / dissociation-reversible group
- Photopolymerization Z dissociative reversible radical R 2 2 is 3 0 O nm or more optical functional group capable dimerization upon exposure to actinic rays having a long wavelength, for example anthranyl group, a pyrimidine base e.g. ⁇ La sills, thymidylate and the like.
- R in the general formula (4) is an alkyl group having 1 to 3 carbon atoms, for example, a methyl, ethyl, propyl or phenyl group. That is, () indicates the monomer unit of an oligoolefin chain, for example, an aliphatic oligoolefin chain such as oligopropylene, oligo (1-butene), or oligo (1-pentene), or an aromatic oligoolefin chain such as styrene.
- the repetition number n is 1 to 100, preferably 10 to 50.
- R 2 2 is a force ⁇ or a R 2 3 group, wherein R 2 3 is hydrogen, hydroxy, alkyl group having 1-8 carbon atoms, such as methyl, Echiru, propyl, Butyl, t-butynole, pentyl, hexinole, cyclohexinole, heptinole, noninole, etc., alkoxy, such as methoxy, ethoxy, propoxy, butoxy, etc. It is a non-functional group.
- the photopolymerization / dissociation-reversible group-containing telechelic oligoolefin is an oligoolefin having one OH group at one end or both ends of the oligoolefin chain represented by the general formula (2a), and an anthrone acid chloride; Alternatively, it can be produced by reacting pyrimidine hydrochloride, peracid hydrochloride or thymine hydrochloride.
- the above-mentioned telechelic oligoolefin containing a photopolymerization / dissociation reversible group is 30 O nm or less.
- the photopolymerized telechelic oligoolefin can be exposed to the above long-wavelength actinic light to be photopolymerized, and the polymerized telechelic oligoolefin is exposed to and / or heated by short-wavelength actinic light of less than 300 nra. Dissociates into telechelic oligoolefins represented by general formula (4).
- the third functional substance of the present invention has the following general formula (5)
- R, n, q, R 2 1 and R 2 2 is defined by the following meanings representing the) photopolymerization Bruno dissociation reversibility represented by the general formula (4) to the repetitive unit
- a functional substance consisting of a polymer obtained by polymerizing two or more molecules of a group-containing telechelic oligoolefin, which is reversibly dissociated by light and / or heat.
- the polymer can be used to convert light having a wavelength of less than 30 O nm into a telechelic oligoolefin represented by the general formula (4) in an appropriate solvent, if necessary, in the presence of a sensitizer. It can be produced by exposure to actinic rays of 30 Onra or more cut with a filter and photopolymerization. Alternatively, the solution can be produced by applying a solution of telechelic oligoolefin onto a substrate, removing the solvent, and exposing the solution to actinic light of 30 O nm or more to photopolymerize the telechelic oligoolefin.
- This polymer well inherits the properties of the oligoolefin constituting the main chain of the telechelic oligoolefin and has substantially the same properties as polyolefin. Therefore, it can be used as a base resin in the production of various molded articles. It can also be expected to be used as a photosensitive polymer utilizing photopolymerizability.
- this polymer can be easily dissociated by exposure to actinic light having a wavelength of less than 30 O nm or by heating, and can reproduce the telechelic oligoolefin represented by the general formula (4). It can be used as a recycled polymer.
- the fourth functional substance of the present invention is: The following general formula (6)
- This polymer is a maleo-oligoolefin (0L-MA) at both ends represented by the general formula (2b) and an oligo-olefin having a hydroxyl group at both ends (0L-0H) represented by the general formula (2a).
- This is a multi-block copolymer in which 0L-MA and 0L-0H are ester-linked.
- R and R 31 in the above formula are each independently an alkyl group having 1 to 3 carbon atoms, for example, a methyl, ethyl, propyl or phenyl group, and the parenthesis shows an oligoolefin chain, for example, oligopropylene, oligo ( It represents a monomer unit of an aliphatic oligoolefin chain such as 1-butene) or oligo (1-pentene) or an aromatic oligoolefin chain such as styrene.
- n and m represent the number of repetitions of the monomer unit. n and m are 1 to 100, preferably 10 to 50.
- the oligoolefin chains of the 0L-MA block and the 0L-0H block may be the same or different.
- Both R and R 31 may be the same in a methyl group, or may be any of an oligopropylene / oligopropylene copolymer having a different number of repetitions ⁇ and m.
- this block copolymer has an ester bond between the blocks, 0L-MA and ⁇ ⁇ Can be hydrolyzed to 0L-OH and has recyclability.
- the above-mentioned copolymerization reaction is a usual esterification reaction between carboxylic anhydride and alcohol, and can be performed by a known method.
- a copolymer can be synthesized by reacting 0L-MA and OL-0H in a toluene solvent in the presence of p-toluenesulfonic acid as a dehydration catalyst.
- the fifth functional substance of the present invention is:
- R in the formula is an alkyl group having 1 to 3 carbon atoms, for example, a methyl, ethyl, propyl or phenyl group.
- R in the formula represents a monomer unit such as an aliphatic oligoolefin chain such as oligopropylene, oligo (1-pentene), or oligo (1-pentene), or an aromatic oligoolefin chain such as oligostyrene, and the number of repetitions n is 1 to 10
- An oligoolefin chain of 0, preferably 10 to 50 is defined as one segment.
- a polycyclic resin having a repeating unit number h of 1 to 100, preferably 10 to 50, preferably 10 to 50, wherein c is 1 to 10, preferably 2 to 6 dimethylsiloxane units having alkylene groups at both ends. Consists of a dimethylsiloxane chain. Both segments are connected via an imide bond.
- the above-mentioned multiblock copolymer is composed of oligoolefin segments and siloxane segments that are incompatible with the oligoolefin segments, so that a multi-phase separation structure is formed. It can be expected to be used in various material fields, such as electric and electronic materials that utilize these properties and the modification of existing resins.
- the multi-block copolymer represented by the general formula (7) can be produced by the following method.
- the diaminoalkylpolydimethylsiloxane represented by the general formula (8) is commercially available in various grades, and can be appropriately selected and used according to the purpose.
- reaction for producing an amic acid from a maleated oligoolefin and a diaminoalkylpolydimethylsiloxane a known reaction for producing a polyamic acid from various tetracarboxylic acids and diamine can be used. Also heating amic acid A reaction for imidization by ring closure is also known.
- the chemical structure of the functional substance according to the present invention is characterized by molecular weight measurement and various spectroscopic measurements.
- the molecular weight and the molecular weight distribution of the obtained polymer can be measured by a generally known genole permeation chromatograph (hereinafter referred to as “GPC”). If necessary, specific parts can be collected and used as samples for detailed analysis (IR, NMR, etc.).
- GPC genole permeation chromatograph
- a more detailed chemical structure can be determined by an infrared absorption spectrum (hereinafter, referred to as “IRJ”), a nuclear magnetic resonance absorption spectrum (hereinafter, referred to as “NMR”), or the like.
- IRJ infrared absorption spectrum
- NMR nuclear magnetic resonance absorption spectrum
- the structure of the functional substance can be qualitatively confirmed by the coexistence of the absorption based on the styrene group and the absorption based on the ether group.
- the absorption intensity based on the group, the absorption intensity based on the ether group, and an appropriate calibration curve the value of the repetition number n of the olefin unit and the repetition number p of the oxyalkylene unit can be determined.
- the structure of a functional substance is qualitatively determined by the coexistence of absorption based on styrene groups (eg, aromatic hydrogen, methylene group, methine group) and absorption based on ether groups (eg, methylene group).
- absorption based on styrene groups eg, aromatic hydrogen, methylene group, methine group
- absorption based on ether groups eg, methylene group.
- Fig. 1 shows the IR spectrum of the pyrolysis product
- Fig. 2 shows the NMR spectrum.
- the 13 C-NMR spectrum of the thermal decomposition product shows the presence of a terminal biylidene group and a saturated terminal methyl group, and the thermal decomposition product has a vinylidene group at both terminals represented by the general formula (1). It was confirmed that the mixture was a mixture of oligo (1-butene) and oligo (1-butene) having a vinylidene group at one end represented by the general formula (2).
- the average number of terminal vinylidene groups per molecule (f TVD value) of the pyrolysis product calculated based on the signal intensity ratio between the side chain methyl group of the terminal vinylidene group and the saturated terminal methyl group is 1.53 to It varied between 1.75.
- Figure 3 1 3 C-NMR spectra show the change of f TVD value with decomposition time in FIG.
- the GPC of the pyrolysis product shows that the number average molecular weight (Mn) and the degree of dispersion of the molecular weight distribution (Mw / Mn) decrease rapidly with the passage of the pyrolysis time, and Mn becomes 100 and Mw / Mn Showed to converge to 1.8.
- Figure 5 shows the changes in Mn and MwZMn with the decomposition time.
- the DSC curve of the pyrolysis product showed that the endothermic peak shifted to a lower temperature with the lapse of decomposition time, and did not show a clear glass transition temperature (Tg).
- Tg clear glass transition temperature
- the onset of weight loss in the TG curve was comparable to that of sample P2000.
- FIG. 6 shows the DSC curve according to the decomposition time
- FIG. 7 shows the TG curve
- FIG. 8 shows the yield of the pyrolysis product.
- Example 1-2 Styrene Dimer (SD) and Trimer (ST) Having One Terminal Vinylidene Group The polystyrene was thermally decomposed at 370 ° C. for 3 hours to obtain a styrene dimer (SD) having one terminal vinylidene group and a trimer (ST). ) Were obtained in a yield of 20 wt% and 30 wt%, respectively.
- Example 2-2 Styrene dimer containing one 0H group at one end (SD-0H) and
- each of the styrene dimer (SD) and the trimer (ST) having a one-end biurydene group obtained in Example 1-2 was dissolved in distilled THF, and a borane THF complex-THF solution was added thereto. For 5 hours with stirring. Hydrogen peroxide and sodium hydroxide were added to each of the obtained THF solutions of hydroborated SD and ST, and the mixture was reacted at a temperature of 50 ° C for 20 hours to obtain a styrene dimer (SD-0H) containing one end—OH group. And a trimer (ST-0H).
- the IR spectrum of the obtained SD-0H is attributed to the terminal buriden group of the raw material SD.
- Example 13 Oligopropylene having bi-endylene group at both ends (iPP-VD) obtained in 13 was dispersed in a THF solvent, and a BH 3 —THF complex ⁇ THF solution was added dropwise, followed by hydroboration in a nitrogen gas atmosphere. After that, the resultant was oxidized with an aqueous NaOH solution and aqueous hydrogen peroxide to convert the terminal bi-lidene group to a hydroxy group, thereby obtaining oligopropylene (iPP-0H) -2 containing both ends of a H0H group.
- Isotactic 'Number-average molecular weight obtained by highly controlled thermal decomposition of polypropylene 1.43x10 Dispersion of molecular weight distribution 1.
- Disperse oligomers (n 34) with bi-ylidene groups at both ends in tetrahydrofuran (THF) among the, after hydroboration both ends Biyuriden group-containing propylene Len oligomer dropwise a THF solution of Betaita 3-THF complex, with the addition of hydroxide Natoriumu solution and peracid hydrogen water at both ends bi
- THF tetrahydrofuran
- THF tetrahydrofuran
- aqueous solution of sodium hydroxide and aqueous hydrogen peroxide were added to oxidize the bilidene groups at both ends, thereby synthesizing oligopropylene (sPPv-OH) containing hydroxy groups at both ends.
- Mn obtained in the above Example 11 has an terminal bililidene group of 3000.
- the molar ratio of maleic anhydride / butylhydroxytoluene (BHT) is 1/10 / 0.5, and the reaction is carried out at 180 ° C for 24 hours in a decahydronaphthalene solvent under a nitrogen gas atmosphere.
- the reaction solution was poured into acetone while hot filtration, and the formed precipitate was filtered by suction and dried under reduced pressure.
- Oligopropylene / dibutylhydroxytoluene / maleic anhydride (BHT) having the bilidene group at both ends of the same lot as used in Example 2-1 was used in a decahydronaphthalene solvent at a molar ratio of 1/42 / 1.68 in a decahydronaphthalene solvent.
- the reaction was performed at ° C for 24 hours.
- the reaction mixture was filtered hot, reprecipitated in acetone, filtered by suction, and dried under reduced pressure to obtain iPP-MA.
- Example 4-1 Oligopropylene Containing Perfluoroalkyl Groups at Both Terminals (iPP-DRF8) iPP-OH-1 synthesized in Example 2-1 and n-CsFi 7 C00H (RF8) were dissolved in a toluene solvent.
- As a catalyst: react for 2 hours in the presence of toluenesulfonic acid while removing water generated under reflux. After completion of the reaction, precipitate the reaction product with methanol. The residue was collected by filtration and dried under reduced pressure to obtain a product.
- Example n- C 8 F 1 7 CH 2 0H (CRF8) and toluene solvent synthesized IPP-MA- 1 and 3 moles the carbonyloxy 1 per 3-2, as a catalyst of p- toluenesulfonic acid The mixture was reacted for 6 hours in the presence while removing water generated under reflux. After completion of the reaction, the reaction product was precipitated with methanol, collected by filtration, and dried under reduced pressure to obtain a product.
- Example 4-3-1 The reaction was carried out under the same conditions as in Example 4-2, except that benzene was used instead of toluene as the reaction solvent in Example 4-12 to lower the reaction temperature.
- 4 - 3 - 2 except using benzene as a reaction solvent, was used IPP-MA- 1 carbonyl one per Ri 2 moles of n- CgFi 7 CH 2 0H (CRF8 ), Example 4 A reaction was performed as in 2.
- the results in Table 1 show that the terminal carboxy group can be left unreacted by selecting a combination of reaction conditions such as reaction temperature, reaction molar ratio, and dehydration conditions during the reaction by selecting a reaction solvent.
- a group having another function for example, a poly (oxyalkylene) group having hydrophilicity can be introduced into the remaining carboxy group according to the purpose.
- an elution peak appeared near Mn: 1500, Mn: near 400, and Mn: 220, which is considered to be the raw material SD-H.
- the eluting peaks around Mn: 1500 and Mn: 400 were separated by recycle GPC and analyzed by IR spectrum.
- the eluting peak near Mn: 1500 was used as a solvent for sodium methoxide.
- the PE0 homopolymer generated starting from the 10H group of methanol used as the starting point, and the elution peak near Mn: 400 can be assigned to SD-PE0.
- the peaks considered to be PE0 homopolymers in SD-PE0-1 were separated and analyzed by measuring the IR spectra of PE0 homopolymer and SD-PE0-1.
- the absorption attributable to the compound clearly appears, and a decrease in the absorption attributable to the phenol unit of the styrene unit near 1800 200 OcnT 1 is observed.
- the results of analysis by separating and separating the peak considered to be SD-PE0-1 clearly show that the absorption due to the ether bond near 110 OcnT 1 appears clearly and 1800 200 No decrease in absorption due to the phenyl group of the styrene cut near O cm- 1 was observed. Similar results are obtained with SD-PE0-2 and ST-PE0. This indicates that the desired copolymer was synthesized.
- Figure 15 shows the 1 H-NMR spectrum of SD-PEO-1.
- a signal due to the aliphatic of the styrene monomer unit around 1.5 to 3 ppm, a signal due to the styrene monomer unit next to the ether bond around 3.5 ppm, and a styrene monomer unit around 7 ppm The signal originated from the aromatic and the signal originated from the E0 monounit appeared around 3.5 to 4 ppm.
- the molar composition ratio of styrene monomer unit: E0 monomer unit determined from the integrated intensity of iH—NMR spectrum was 2: 5.
- the molar composition ratios of styrene mono-unit: E0 monomer unit were as follows: SD-PE0-2: 2:17, ST-PE0 was 3:29. From the above, it can be seen that the target copolymer was synthesized.
- Figure 16 shows the concentration dependence of the surface tension of each copolymer aqueous dispersion.
- the surface tension decreased as the concentration increased, and 0.3 g / L for SD-PEO-1 and 0.2 g / L for SD-PEO-2, and ST-PEO.
- CMC critical micelle concentration
- Fig. 17 shows the concentration dependence of the average particle size of micelles in each copolymer dispersion. As the concentration increases in each of the copolymers, the particle size decreases, but the particle size increases after CMC.
- the average particle size of micelles in each copolymer dispersion is about 140 nm for SD-PE0-1, about 70 nm for SD-PE0-2, about 130 nm for ST-PE0, It is considered that extremely large molecular aggregates are formed, 27 times, 5 times, and 6 times the extended chain length of each copolymer molecule. From the results of the particle size measurement, the formed molecular aggregate is not a simple micellar structure, but a hydrophilic group and a hydrophobic group that are superimposed on each other due to the hydrophobic interaction of styrene unit. It was thought to form an aggregate. It is considered that the structure forms a bimolecular film or a multimolecular film of more.
- Styrene dimer containing terminal perfluoroalkyl group (SD-PE0-R f)
- a perfluoroalkyl group was esterified at the end of SD-PE0 by an esterification reaction between SD-PE0, which was prepared separately and shown in Table 3, and a perfluoroalkyl carboxylic acid having 7 to 18 carbon atoms (Rf-C00H).
- Rf-C00H a perfluoroalkyl carboxylic acid having 7 to 18 carbon atoms
- the molecular weight distribution of the obtained SD-PEO-Rf was unimodal, and shifted to higher molecular weights as compared to SD-PEO.
- the M n is 1. 2 8 X 1 0 3
- M wZMn was 1. 0 7.
- the IR spectrum of SD-PEO-Rf shows that broad absorption derived from hydroxyl group near 3400 cm- 1 decreases, and that 8 O cm- 1 near the absorption due to ester group, and absorption due to the 1 2 1 0 cm one 1 fluorine group near appeared.
- Figure 19 shows the surface tension of SD-PE0 and SD-PEO-Rf aqueous dispersions. As the concentration increased, the surface tension decreased in both cases, confirming the critical micelle concentration (CMC). The CMC was around 0.3 g / L for SD-PE0 and around 0.1 g / L for SD-PEO-Rf. 1 The surface tension was about 44 and about 28 mNZm, respectively. A large hydrophobic interaction of the terminal-Rf group with respect to the decrease in surface tension was observed.
- CMC critical micelle concentration
- Example 4 1-5 Oligopropylene having a perfluoroalkyl group at both terminals /
- Sodium methoxide was dispersed as a catalyst in a toluene solution of oligopropylene (iPP-OH-2) having a terminal group at both ends synthesized in Example 2-3, and the reaction temperature was set to 130 under a nitrogen gas atmosphere. While controlling the internal pressure at ° C, ethylenoxide was added dropwise per mole of the olefin polymer to cause a reaction. The resulting reaction product was heated under acetone reflux, and then separated at room temperature into acetone-soluble and insoluble components. Then acetone soluble components The polymer was fractionated by recycling GPC.
- the ratio of oxyethylene units to propylene units [Z pZn] calculated from the integrated intensity ratio of 1 H-NMR of the obtained triblock polymer was 0.86.
- the number average molecular weight (Mn) (in terms of polystyrene) by GPC was 2.15 ⁇ 10 3 , Mw / Mn was 1.07, and the melting point (Tm) by DSC was 104 to 124 ° C.
- Table 4 shows the evaluation results of (iPPOH).
- FIG. 20 shows GPC curves of iPP-b-PE0, iPPV and iPPOH
- FIG. 21 shows 13 C-NMR spectra of iPPOH and iPP-b-PE0.
- the vertical axis represents the reading on the scale of the surface tensiometer, and the horizontal axis represents the concentration (mgZml) of the triblock copolymer in the aqueous solution.
- the vertical axis in FIG. 22 represents the relative surface tension based on water, and shows that even a small amount of the triploc copolymer significantly reduces the surface tension of the aqueous solution.
- Fig. 23 shows the particle size distribution of a triploc copolymer dispersion in an aqueous medium measured at 25 using the cumulant method for measuring dynamic light scattering (DLS) with a He-Ne laser. .
- CM C critical micelle concentration
- Poly (oxyethylene) triblock copolymer 2 iPP-b-PE0-Rf
- Ring-opening polymerization of ethylene oxide iPP-b-PEO
- Triblock copolymers of isotactic oligopropylene and oligo (ethylene oxide) form large molecular aggregates in aqueous dispersions,
- the particle size measured by DLS is E0 As the percentage of segments increased, they tended to grow.
- Triploc copolymer 2 (iPP-b-PEO-Rf)
- iPP-b- PEO-Rf is the IR spectrum
- iPP-b-PEO end absorption from the hydroxyl group of (3 4 0 0 cm one 1 near) is significantly reduced
- Karupoyuru from (1 8 0 0 cm near one 1) the absorption from ⁇ Pi fluorine group (1 2 0 0 cm- near 1) is newly appeared.
- Fig. 24 shows the IR spectrum of Triplop copolymer 2 (iPP-b-PE0-Rf).
- iPP-b-PE0-Rf triblock copolymer 2
- THF dispersion of iPPv-0HZ triethylamine prepared in Example 2-4 a THF dispersion of anthrone acid chloride was added dropwise at room temperature under a nitrogen atmosphere, and the reaction was aged for 2 hours. Then, THF was distilled off from the reaction solution, xylene was added to dissolve the solution under reflux, filtered by hot filtration, dropped into methanol, precipitated, and collected by filtration. The yield of the precipitate was about 90% by weight.
- Figure 26 shows the ifi-NMR spectra of iPPv-AR and iPPv-0H.
- the GPC curve of the reaction mixture is shown in FIG. As is clear from FIG. 27, as the time elapses, the peak of the monomer decreases, and instead, peaks indicating the formation of dimers, trimers, and tetramers appear.
- the polymerization reaction rate obtained from the area ratio 18 hours after light irradiation was 86%.
- the iPPv-AT polymer solution obtained after the elapse of the photopolymerization reaction time was irradiated with light having a wavelength of less than 30 Onra by cutting light of 30 On Ra or more through an optical filter using a high-pressure mercury lamp.
- the polymer was dissociated by irradiation.
- THF dispersion of anthrone acid chloride was added dropwise at room temperature under a nitrogen atmosphere, and the reaction was further aged for 2 hours. Then, THF was distilled off from the reaction solution, xylene was added to dissolve the solution under reflux, filtered by hot filtration, dropped into methanol, precipitated, and collected by filtration. The yield of the precipitate is about 90 weight 0 /. Met.
- a light of less than 30 nm was cut through a filter of naphthalene hexane solution into a solution of 0.2 ⁇ sPPv-AT dissolved in 11
- the sPPv-AT was polymerized by irradiation with light having the above wavelength.
- the reaction became cloudy over time, but became clear upon addition of additional THF.
- the GPC curve of the reaction mixture is shown in FIG.
- the reaction time increased, the molecular weight gradually increased.
- the molecular weight distribution of sPPv-AT did not change, and photosequential polymerization stopped. Comparing the peak top and number average molecular weight of the sequential polymer obtained at 0 hours and 12 hours, the peak top is about 6 times and the number average molecular weight is about 3 times. This revealed that the anthracene groups at both ends of sPPv-AT were sequentially polymerized by light.
- FIG. 29 shows a GPC curve when a polymer obtained by photo-sequentially polymerizing sPPv-AT for 18 hours was placed in a polymerization tube, and the product sealed with nitrogen was heated at 140 ° C. for 2 hours. The figure shows that the photo-sequential polymer is completely dissociated into sPPv-AT by heat.
- IPP-0H, 3 0 the iPP-MA and IPP-b-iPP of IR scan Bae spectrum shows the iPP-MA and IPP-b-iPP of 13 C-NMR scan Bae spectrum in FIG 1.
- Figure 32 shows the GPC curves of iPP-0H, iPP-MA and iPP-b-iPP with different reaction times.
- IPP-MA synthesized in Example 3-3 and diaminoalkyl polydimethylsiloxane A commercial product was treated with methanol to remove low molecular weight components.
- the molar ratio to diaminoalkyl polydimethylsiloxane (PDMS) with a number average molecular weight of 50,000 was set to 1/1, and the decalin solvent was used in a nitrogen gas atmosphere. After stirring at 60 ° C for 10 minutes, imidization was carried out by stirring at 190 ° C for 0.5, 6, 24 and 48 hours. Was added thereto, and the precipitate was collected by filtration and dried under reduced pressure to obtain a product.
- PDMS diaminoalkyl polydimethylsiloxane
- the 1 H-NMR spectrum confirmed that the product was a multi-block copolymer (iPP-PDMS).
- the iPPunit ZPDMS unit molar ratio calculated from the signal intensity ratio between the iPPunit and the PDMSunit was 44.6Z55.4 in the 24-hour reaction, and 40.359.7 in the 48-hour reaction. Met.
- Figure 33 shows the NMR spectrum of iPP-PDMS.
- the GPC curve of iPP-PDMS obtained by the reaction for 24 hours and 48 hours is unimodal, the number average molecular weight of iPP-PDMS is about 800, and the dispersibility of molecular weight distribution Mw / Mn is 1.87.
- Fig. 34 shows the GPC curves of iPP-PDMS, iPP-MA and PDMS superimposed.
- Functional substances of the present invention contain per full O b group without via or through the poly (O Kishiarukiren) chains at both terminals or one terminal of Origoorefuin chain lipophilic supercritical C0 2 affinity If necessary, an amphiphilic functional substance having hydrophilicity, a photopolymerizable functional substance containing a photopolymerization / dissociation-reversible group at both or one end of the oligoolefin chain, and the photopolymerizable A functional substance consisting of a photo- and / or heat-dissociable polymer obtained by photopolymerizing a functional substance, and a hydrolyzable functionality consisting of a polymer in which multiple oligoolefin chains are chain-extended by an ester bond. Substances and polymerlays in which polyimide chains and polydimethylsiloxane chains are imidically bonded
- Amphiphilic functional substance is not only available supercritical C0 2 as a reaction solvent can be widely used as various surfactants in the existing art.
- Photopolymerization Z-dissociative reversible group-containing functional material and light composed of the polymer and Z- or heat-dissociable functional material and hydrolyzable functional material can be used as recycled polymer Not only that, it can be used for molded articles having properties equivalent to those of the starting polyolefin.
- the Miku phase-separated structure-forming functional material can be used for functional products such as electronic materials.
- These functional substances are characterized by containing a segment consisting of an oligoolefin chain, and this segment modifies the terminal biylidene double bond of the oligoolefin containing a terminal vinylidene group obtained by highly controlled pyrolysis of polyolefin. Derived from terminally functional oligoolefins with functional groups introduced. As a result, all of the functional substances have properties that reflect the properties of the starting polyolefin.
- the oligo (1-butene) having a vinylidene terminal group at the terminal of the present invention can be used as a raw material for synthesizing the functional substance of the present invention.
- the starting polyolefin does not need to be fresh polyolefin, but can use waste pellets that pose environmental problems.
- the present invention provides a new use of polyolefin, but the above are only some examples, and further development of functional materials is expected.
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EP01997195A EP1364973B1 (en) | 2000-11-24 | 2001-11-22 | Functional substances derived from oligoolefins having functional groups at the ends |
US10/416,615 US7125834B2 (en) | 2000-11-24 | 2001-11-22 | Functional substances derived from oligoolefins having functional groups at the ends |
DE60143490T DE60143490D1 (de) | 2000-11-24 | 2001-11-22 | Von oligoolefinen mit funktionellen endgruppen abgeleitete funktionelle substanzen |
AU2002224085A AU2002224085A1 (en) | 2000-11-24 | 2001-11-22 | Functional substances derived from oligoolefins having functional groups at the ends |
KR10-2003-7006981A KR100501968B1 (ko) | 2000-11-24 | 2001-11-22 | 말단 관능성기를 갖는 올리고올레핀으로부터 유도되는기능성 물질류 |
HK04110142.2A HK1067135A1 (en) | 2000-11-24 | 2004-12-22 | Functional substances derived from oligoolefins having functional groups at the ends |
US11/440,900 US7229957B2 (en) | 2000-11-24 | 2006-05-25 | Functional substances derived from oligoolefins having functional groups at the ends |
US11/654,751 US7345017B2 (en) | 2000-11-24 | 2007-01-18 | Functional substances derived from oligoolefins having functional groups at the ends |
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JP2000358226A JP4118504B2 (ja) | 2000-11-24 | 2000-11-24 | ポリオレフィン/ポリオレフィン・ブロック共重合体 |
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JP2000358227A JP4790112B2 (ja) | 2000-11-24 | 2000-11-24 | 末端パーフルオロアルキル基含有オレフィン・オリゴマーおよびその製造方法 |
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JP2000358225A JP4686022B2 (ja) | 2000-11-24 | 2000-11-24 | 末端マレイン化オリゴオレフィン/ジアミノポリジメチルシロキサン・マルチブロック共重合体およびその製造方法 |
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JP2001331937A JP4124586B2 (ja) | 2000-11-24 | 2001-10-30 | 光重合/解離可逆性テレケリックオリゴマーおよびその重合体ならびにそれらの製造方法 |
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JP2001340118A JP4125884B2 (ja) | 2001-11-06 | 2001-11-06 | 末端ビニリデン基を有するオリゴ(1−ブテン) |
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---|---|---|---|---|
WO2003082957A1 (fr) * | 2002-03-29 | 2003-10-09 | San-Ei Kougyou Corporation | Nouveau copolymere sequence polyesterifie et son procede de production |
JP2005097588A (ja) * | 2003-08-27 | 2005-04-14 | Mitsui Chemicals Inc | 両末端官能性ポリオレフィン |
EP1666507A1 (en) * | 2003-08-27 | 2006-06-07 | Mitsui Chemicals, Inc. | Polyolefin functional at each end |
JP2006307191A (ja) * | 2005-03-29 | 2006-11-09 | Mitsui Chemicals Inc | ビシナル置換型官能基含有重合体及びその用途 |
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DE60143490D1 (de) * | 2000-11-24 | 2010-12-30 | Takashi Sawaguchi | Von oligoolefinen mit funktionellen endgruppen abgeleitete funktionelle substanzen |
JP4012058B2 (ja) * | 2001-12-21 | 2007-11-21 | キヤノン株式会社 | リサイクル性重合体、その製造方法、ならびにリサイクル処理方法 |
WO2006113666A2 (en) * | 2005-04-19 | 2006-10-26 | Massachusetts Institute Of Technology | Amphiphilic polymers and methods of use thereof |
KR101061686B1 (ko) * | 2007-07-02 | 2011-09-01 | 미쓰이 가가쿠 가부시키가이샤 | 극성기 함유 폴리올레핀 중합체 및 그의 제조방법과, 수분산체 및 이형제 조성물 |
EP2578607A4 (en) | 2010-05-26 | 2014-01-22 | Idemitsu Kosan Co | TERMINAL-UNSATURATED POLYOLEFIN AND PROCESS FOR PRODUCING THE SAME |
JP6545497B2 (ja) * | 2015-03-25 | 2019-07-17 | 三井化学株式会社 | 硬化性組成物およびその製造方法 |
CN107892897B (zh) * | 2017-12-12 | 2020-11-10 | 苏州铂邦胶业有限公司 | 一种强黏结力硅酮密封胶及其制备方法 |
WO2019162493A1 (en) * | 2018-02-23 | 2019-08-29 | Solvay Specialty Polymers Italy S.P.A. | Fluorinated monomers comprising anthracene moieties |
EP3902808A1 (en) * | 2018-12-28 | 2021-11-03 | Dow Global Technologies LLC | Curable compositions comprising unsaturated polyolefins |
SG11202107071XA (en) * | 2018-12-28 | 2021-07-29 | Dow Global Technologies Llc | Curable compositions comprising telechelic polyolefins |
CN112142885B (zh) * | 2020-09-07 | 2022-07-12 | 万华化学集团股份有限公司 | 一种低温下溶液稳定性优异的低氯氯化聚丙烯及其制备方法 |
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JPS5584302A (en) | 1978-12-20 | 1980-06-25 | Takashi Sawaguchi | Preparation of alpha,omega-diene-oligomer |
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DE60143490D1 (de) * | 2000-11-24 | 2010-12-30 | Takashi Sawaguchi | Von oligoolefinen mit funktionellen endgruppen abgeleitete funktionelle substanzen |
-
2001
- 2001-11-22 DE DE60143490T patent/DE60143490D1/de not_active Expired - Lifetime
- 2001-11-22 WO PCT/JP2001/010244 patent/WO2002042340A1/ja active IP Right Grant
- 2001-11-22 CN CN200810181676XA patent/CN101486779B/zh not_active Expired - Fee Related
- 2001-11-22 CN CNB01819429XA patent/CN100558758C/zh not_active Expired - Fee Related
- 2001-11-22 AU AU2002224085A patent/AU2002224085A1/en not_active Abandoned
- 2001-11-22 KR KR10-2003-7006981A patent/KR100501968B1/ko not_active IP Right Cessation
- 2001-11-22 EP EP01997195A patent/EP1364973B1/en not_active Expired - Lifetime
- 2001-11-22 DE DE60137463T patent/DE60137463D1/de not_active Expired - Lifetime
- 2001-11-22 US US10/416,615 patent/US7125834B2/en not_active Expired - Fee Related
- 2001-11-22 EP EP07001650A patent/EP1790669B1/en not_active Expired - Lifetime
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2004
- 2004-12-22 HK HK04110142.2A patent/HK1067135A1/xx not_active IP Right Cessation
- 2004-12-22 HK HK09110762.6A patent/HK1133025A1/xx not_active IP Right Cessation
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2006
- 2006-05-25 US US11/440,900 patent/US7229957B2/en not_active Expired - Fee Related
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JPH0892312A (ja) * | 1994-09-22 | 1996-04-09 | Res Dev Corp Of Japan | 末端に定量的にビニリデン基を有する高分子化合物、その製造方法及び該高分子化合物を使用したレジスト材 |
JP2001098022A (ja) * | 1999-07-23 | 2001-04-10 | Takashi Sawaguchi | 末端ビニリデン基含有スチレン系重合体、その製造方法及びそれを含有する樹脂組成物 |
JP2002060425A (ja) * | 2000-08-18 | 2002-02-26 | Toagosei Co Ltd | マクロモノマーの製造方法 |
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Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2003082957A1 (fr) * | 2002-03-29 | 2003-10-09 | San-Ei Kougyou Corporation | Nouveau copolymere sequence polyesterifie et son procede de production |
US7452939B2 (en) | 2002-03-29 | 2008-11-18 | San-Ei Kougyou Corporation | Polyesterified block copolymer and process for producing the same |
JP2005097588A (ja) * | 2003-08-27 | 2005-04-14 | Mitsui Chemicals Inc | 両末端官能性ポリオレフィン |
EP1666507A1 (en) * | 2003-08-27 | 2006-06-07 | Mitsui Chemicals, Inc. | Polyolefin functional at each end |
EP1666507A4 (en) * | 2003-08-27 | 2008-07-30 | Mitsui Chemicals Inc | BOTH END FUNCTIONAL POLYOLEFIN |
JP2009155656A (ja) * | 2003-08-27 | 2009-07-16 | Mitsui Chemicals Inc | 両末端官能性ポリオレフィン |
US8017693B2 (en) | 2003-08-27 | 2011-09-13 | Mitsui Chemicals, Inc. | Polyolefin functional at each end |
US8129475B2 (en) * | 2003-08-27 | 2012-03-06 | Mitsui Chemicals, Inc. | Telechelic polyolefin |
JP2006307191A (ja) * | 2005-03-29 | 2006-11-09 | Mitsui Chemicals Inc | ビシナル置換型官能基含有重合体及びその用途 |
Also Published As
Publication number | Publication date |
---|---|
CN101486779A (zh) | 2009-07-22 |
EP1790669A2 (en) | 2007-05-30 |
CN1525984A (zh) | 2004-09-01 |
KR100501968B1 (ko) | 2005-07-20 |
AU2002224085A1 (en) | 2002-06-03 |
HK1133025A1 (en) | 2010-03-12 |
HK1067135A1 (en) | 2005-04-01 |
DE60137463D1 (de) | 2009-03-05 |
US20060211595A1 (en) | 2006-09-21 |
US20040022757A1 (en) | 2004-02-05 |
EP1790669A3 (en) | 2007-10-31 |
US7125834B2 (en) | 2006-10-24 |
US7345017B2 (en) | 2008-03-18 |
EP1364973B1 (en) | 2010-11-17 |
CN101486779B (zh) | 2011-01-26 |
DE60143490D1 (de) | 2010-12-30 |
US20070117738A1 (en) | 2007-05-24 |
KR20030053534A (ko) | 2003-06-28 |
US7229957B2 (en) | 2007-06-12 |
EP1364973A1 (en) | 2003-11-26 |
EP1790669B1 (en) | 2009-01-14 |
CN100558758C (zh) | 2009-11-11 |
EP1364973A4 (en) | 2006-05-03 |
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