CN101395197A - Norbornene-ester polymer containing bulky substituents - Google Patents

Norbornene-ester polymer containing bulky substituents Download PDF

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CN101395197A
CN101395197A CNA2007800073284A CN200780007328A CN101395197A CN 101395197 A CN101395197 A CN 101395197A CN A2007800073284 A CNA2007800073284 A CN A2007800073284A CN 200780007328 A CN200780007328 A CN 200780007328A CN 101395197 A CN101395197 A CN 101395197A
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norbornylene
methyl
ester polymer
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白守珉
金炫辰
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Kolon Industries Inc
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Abstract

This invention provides a norbornene-ester polymer, obtaining by a norbornene-ester monomer having a total number of carbons of the ranges from 19 to 80, having a bulky substituent.

Description

Contain the substituent norbornylene-ester polymer of large volume
Technical field
The present invention relates to a kind of norbornylene-ester polymer, more specifically, relate to a kind of by having norbornylene-ester polymer that the substituent norbornene monomer of large volume obtains with ester group.
Background technology
Usually, as the material of insulation component, mainly use as inorganic materials such as silicon-dioxide or silicon nitrides always.But, caused specific inductivity to the demand of growth and hydroscopicity is lower and metal tackiness, intensity, thermostability and transmittance are good and have the demand of the polymkeric substance of high glass transition with high efficiency littler device.
Current, polyimide or BCB (two benzocyclobutene) are as the low dielectric material of electronic material.Polyimide has excellent thermostability and oxidative stability, high glass-transition temperature and good mechanical property, thereby has been widely used in electronic material.But, because polyimide owing to high-hygroscopicity, anisotropic electrology characteristic, need carry out pre-treatment and have with corrosion of elements and specific inductivity with the reactive of copper cash and with the tackiness of metal and increase relevant problem, so it affects adversely to reduce it.And, although comparing with polyimide, BCB has lower hydroscopicity and lower specific inductivity, also there is the problem that the metal tackiness is relatively poor and the solidification process need carry out at high temperature in it.
Therefore, carried out using the trial of cyclic olefin polymer.
Cyclic olefin polymer is the polymkeric substance that obtains by the polymerization as cycloolefin monomers such as norbornylenes, and it has the good transparency, thermotolerance and chemical resistant properties, in addition, compares with traditional olefin polymer and also to have much lower degree of birefringence and water absorbability.Therefore; this polymkeric substance can be used for the insulating film of semi-conductor or TFT-LCD, protective membrane, mcm, IC, printed circuit board (PCB), electronic material or the low dielectric coating material encapsulant of sealing agent, film and flat-panel monitor or optics of polaroid, also can be used as the material of the plastic-substrates of flexible display.
But, for norbornene polymer being used for above-mentioned end-use, must guarantee higher optical characteristics and thermostability.The transmittance of current commercially available norbornene polymer is about 80%～90%, and second-order transition temperature (Tg) is 100 ℃～180 ℃, and this can not satisfy realizes the requirement of above-mentioned end-use to characteristic.
In cycloolefin monomers contains situation such as ester group isopolarity functional group, this polar functional group is played a role to the tackiness aspect of metal base or other polymkeric substance to increasing intermolecular accumulation and increasing, can be used for the information electronic material effectively, therefore, polymerization or copolymerization with norbornylene of ester group constantly are subjected to increasing concern (United States Patent (USP) 3,330, No. 815, EP0445755A2, No. 5,705,503, United States Patent (USP), United States Patent (USP) 6,455, No. 650).
Yet,, still have the problem that can not guarantee optical characteristics and thermostability even contain this polar functional group.
The Korean unexamined patent communique discloses a kind of thermostability and oxidative stability and high chemical resistance and the adhesive norbornylene of metal-ester addition polymer and preparation method thereof with low-k, low hydroscopicity, high glass-transition temperature, excellence for 2004-5593 number.This norbornylene-ester addition polymer comprises norbornylene-ester monomer (exo isomer, exo isomer) of 50mol% at least, and as repeating unit, molecular weight is at least 20,000.
Although measured the metal tackiness and the surface tension of this addition polymer and tackiness and the degree of birefringence of utilizing the film of this addition polymer, not mentioned hydroscopicity, the stability that comprises thermostability and optical characteristics in above-mentioned patent.After all, above-mentioned patent is unfavorable for addressing the above problem.And, although should be more than the 50mol%, be difficult to guarantee the monomer of this amount as the monomeric consumption of the norbornylene-ester of exo isomer.
Summary of the invention
Technical problem
According to an embodiment of the invention, a kind of norbornylene-ester polymer is provided, thereby wherein said norbornylene-ester monomer comprises the large volume substituting group and has improved second-order transition temperature, thereby the optical material that comprises this polymkeric substance demonstrates excellent optical and thermal characteristic.
The purpose of this invention is to provide a kind of norbornylene-ester polymer, described polymkeric substance can improve thermostability and transmittance, and water absorbability is minimized.
Technical scheme
According to an embodiment of the invention, the invention provides a kind of norbornylene-ester polymer, i) carbon that comprises by following formula 1 expression of described norbornylene-ester polymer adds up to norbornylene-ester cpds repeating unit of 19～80; And ii) the transmittance of described norbornylene-ester polymer is more than 0.9, described transmittance is measured in the following manner: with described polymer formation is casting films, use turbidometer to measure this casting films at the wavelength place of 400nm～800nm then, determine transmittance according to following equation 1 again in the optical absorption intensity of suprabasil vertical incidence light intensity, this substrate and the luminous reflectance intensity of this substrate:
Formula 1
Figure A200780007328D00061
Wherein, R 1, R 2And R 3, can be same to each other or different to each other the hydrogen atom of respectively doing for oneself, C 1～10Straight or branched alkyl or C 5～12Cycloalkyl, R 1, R 2And R 3In at least one be not hydrogen atom, R 4Have and be selected from
Figure A200780007328D00062
With In structure, wherein, R 5Be hydrogen atom, C 1～10Straight or branched alkyl or C 5～12Cycloalkyl, n is the integer more than 0; With
Equation 1
l 0 - ( l a + l r ) l 0 = T
Wherein, l 0Be at suprabasil vertical incidence light intensity, l aBe the optical absorption intensity of this substrate, l rBe the luminous reflectance intensity of this substrate.
According to the present invention, the second-order transition temperature of described norbornylene-ester polymer (Tg) can be 200 ℃～300 ℃.
The number-average molecular weight of described norbornylene-ester polymer (Mn) can be for more than 10,000, and molecular weight distribution can be 1.0～4.0.
In addition, the invention provides a kind of optical material, described optical material comprises described norbornylene-ester polymer.
Described optical material is characterised in that the transmittance of determining according to equation 1 is more than 0.9.
Described optical material can be a film.
Beneficial effect
According to the present invention, norbornylene-ester polymer has high glass-transition temperature (thereby demonstrating excellent thermostability), has the good metal tackiness, transmittance (thereby having realized good optical characteristics) with raising, have MIN water absorbability, thereby make it be easy to prepare electronic material.
Embodiment
Below, the present invention is described in detail.
Norbornylene-ester polymer of the present invention obtains by making the norbornylene with 19～80 carbon-ester monomer polymerization by following formula 1 expression, and described monomer is that ester group and large volume substituting group are introduced the ring-type norbornene monomer.
Tangle or become accumulation mutually if polymer chain becomes, transmittance may reduce.Polymkeric substance of the present invention is characterised in that this monomer itself that constitutes repeating unit adds the large volume substituting group, thereby the accumulation of the chain of resulting polymers is few, and perhaps stackeding space increases, thereby has prevented the entanglement phenomenon, causes transmittance to rise.
Term " norbornylene-ester monomer " refers to contain the unitary monomer of norbornylene (dicyclo [2,2,1] hept-2-ene") shown at least one the following formula 2:
Formula 2
Figure A200780007328D00071
Norbornylene shown in the formula 1-ester monomer can by make be substituted with alkyl or unsubstituted cyclopentadiene (CPD), Dicyclopentadiene (DCPD) (DCPD) or their mixture carry out diels-alder reaction with alkyl acrylate and obtain with adamantyl.
Particularly, be substituted with alkyl or unsubstituted CPD, DCPD or their mixture and the molar ratio reaction of the alkyl acrylate with adamantyl with 1:0.5～10 (preferred 1:0.5～4), thereby described norbornylene-ester monomer obtained.
So, temperature of reaction is set at 180 ℃～220 ℃, reaction pressure is set at more than the normal atmosphere.
Behind the monomer that synthesizes formula 1, can add polymerization retarder and be adjusted to required numerical value with n with formula 1.The specific examples of described polymerization retarder is including, but not limited to aniline, hexanaphthene, phenol, 4-epoxy phenol, oil of mirbane, quinhydrones, benzoquinones, dichloride copper and 2, and 2-two (uncle's 4-octyl phenyl)-1-picrylhydrazyl preferably uses quinhydrones or benzoquinones.
Adding described polymerization retarder, is 1:0.001～0.05 so that be substituted with mol ratio alkyl or unsubstituted CPD, DCPD or their mixture and described polymerization retarder, is preferably 1:0.002～0.04.
The monomer that so obtains preferably can have following structure as shown in Equation 1: in formula 1, and R 1～R 3In at least one, R particularly 1, be not hydrogen atom.Such structure is included as repeating unit in polymkeric substance, thereby works to increase the amorphism of polymkeric substance, causes transmittance to rise.
When above-mentioned monomer polymerization is polymkeric substance, according to typical norbornene polymerization method, polymerizable monomer and catalyzer are mixed with organic solvent, in addition, can add promotor in case of necessity.
As organic solvent, alcohol can use separately, also can combination water or the organic solvent (as tetrahydrofuran (THF)) except that alcohol use, pure example comprises methyl alcohol, ethanol, Virahol and butanols.
The example of catalyzer comprises transition-metal catalyst, as nickel and palladium, and Metallocenic compound.
In that polymerization temperature (becoming according to type of solvent) is maintained in 20 ℃～100 ℃, react 1～24 hour, thereby make norbornylene-ester polymer.
The number-average molecular weight with the substituent norbornylene-ester polymer of large volume (Mn) that so makes is more than 10,000.Under typical polymerizing condition, Mn is 20,000～1,000,000, and molecular weight distribution is 1.0～4.0.
Because the second-order transition temperature of described norbornylene-ester polymer is 200 ℃～300 ℃, so it can be used in the high thermal stability material, also has the metal tackiness that is equal to or higher than traditional norbornylene-ester polymer.
Further, will have the substituent described norbornylene-ester polymer of large volume and be dissolved in the solvent, then by solvent cast legal system film forming or sheet.So, described polymkeric substance can use with one or more mixture.The thickness of prepared film is 50 μ m～500 μ m, and transmittance is more than 0.9, and described transmittance is determined according to following equation 1:
Equation 1
l 0 - ( l a + l r ) l 0 = T
Wherein, l 0Be at suprabasil vertical incidence light intensity, l aBe the optical absorption intensity of this substrate, l rBe the luminous reflectance intensity of this substrate.
And described film or sheet have agent of low hygroscopicity, have therefore realized good dimensional stability.
Embodiment
By following embodiment, the present invention may be better understood, and setting forth described embodiment is to be used for explanation, and described embodiment should not be interpreted as limitation of the present invention.
Norbornylene-ester monomeric synthetic (synthesis example 1～8, contrast synthesis example 1～2)
＜synthesis example 1〉2-methyl-2-adamantyl-5-norbornylene-2-methyl-2-carboxylicesters synthetic
In the 0.25L autoclave, add DCPD (Dicyclopentadiene (DCPD), Aldrich, 10.2ml, 0.0757mol), methacrylic acid 2-methyl-2-adamantane esters (42.6g, 0.18mol) and quinhydrones (0.83g, 0.1mol), make then its 180 ℃ the reaction 12 hours, after the reaction product cooling, transfer in the water distilling apparatus, use vacuum pump under the decompression of 1 holder, to distill then, thereby obtain the finished product (productive rate: 25%) at 110 ℃.The mol ratio (mol%) of the exo isomer of this product and endo isomer (endoisomer) is 48.5:51.5.
1H-NMR (500MHz, CDCl 3), interior type: δ 6.20 (dd, 1H), 6.18 (dd, 1H); External form: δ 6.12 (m, 2H)
＜synthesis example 2〉2-ethyl-2-adamantyl-5-norbornylene-2-methyl-2-carboxylicesters synthetic
In the 0.25L autoclave, add DCPD (Dicyclopentadiene (DCPD), Aldrich, 10.2ml, 0.0757mol), methacrylic acid 2-ethyl-2-adamantane esters (44.3g, 0.18mol) and quinhydrones (0.83g, 0.1mol), make then its 200 ℃ the reaction 12 hours, after the reaction product cooling, transfer in the water distilling apparatus, use vacuum pump under the decompression of 1 holder, to distill then, thereby obtain the finished product (productive rate: 27%) at 120 ℃.The exo isomer of this product and the mol ratio of endo isomer (mol%) are 45.5:54.2.
1H-NMR (500MHz, CDCl 3), interior type: δ 6.22 (dd, 1H), 6.19 (dd, 1H); External form: δ 6.18 (m, 2H)
＜synthesis example 3〉2-methyl-2-adamantyl-5-norbornylene-2-ethyl-2-carboxylicesters synthetic
In the 0.25L autoclave, add DCPD (Dicyclopentadiene (DCPD), Aldrich, 10.2ml, 0.0757mol), ethylacrylic acid 2-methyl-2-adamantane esters (44.3g, 0.18mol) and quinhydrones (0.83g, 0.1mol), make then its 210 ℃ the reaction 12 hours, after the reaction product cooling, transfer in the water distilling apparatus, use vacuum pump under the decompression of 1 holder, to distill then, thereby obtain the finished product (productive rate: 34%) at 117 ℃.The exo isomer of this product and the mol ratio of endo isomer (mol%) are 40.2:59.5.
1H-NMR (500MHz, CDCl 3), interior type: δ 6.20 (dd, 1H), 6.18 (dd, 1H); External form: δ 6.14 (m, 2H)
＜synthesis example 4〉1-adamantyl-5-norbornylene-2-methyl-2-carboxylicesters synthetic
In the 0.25L autoclave, add DCPD (Dicyclopentadiene (DCPD), Aldrich, 10.2ml, 0.0757mol), methacrylic acid 1-adamantane esters (40.0g, 0.18mol) and quinhydrones (0.83g, 0.1mol), make then its 200 ℃ the reaction 12 hours, after the reaction product cooling, transfer in the water distilling apparatus, use vacuum pump under the decompression of 1 holder, to distill then, thereby obtain the finished product (productive rate: 85%) at 100 ℃.The exo isomer of this product and the mol ratio of endo isomer (mol%) are 40.0:59.1.
1H-NMR (500MHz, CDCl 3), interior type: δ 6.18 (dd, 1H), 6.04 (dd, 1H); External form: δ 6.12 (dd, 1H), 6.04 (dd, 1H)
＜synthesis example 5〉2-methyl-2-adamantyl-9-tetracyclododecane-4-methyl-4-carboxylicesters synthetic
In the 0.25L autoclave, add DCPD (Dicyclopentadiene (DCPD), Aldrich, 10.2ml, 0.0757mol) and methacrylic acid 2-methyl-2-adamantane esters (42.6g, 0.18mol), make it 180 ℃ of reactions 12 hours then, adding DCPD (Dicyclopentadiene (DCPD) to the gained reaction solution, Aldrich, 5.1ml, 0.0379mol) afterwards, make it then 200 ℃ of reactions 8 hours.With the reaction product cooling, transfer in the water distilling apparatus, use vacuum pump under the decompression of 1 holder, to distill then, thereby obtain the finished product (productive rate: 25%) at 110 ℃.The exo isomer of this product and the mol ratio of endo isomer (mol%) are 47.5:52.5.
1H-NMR (500MHz, CDCl 3), interior type: δ 6.30 (dd, 1H), 6.18 (dd, 1H), 2.32 (dd, 2H); External form: δ 6.20 (m, 2H), 2.40 (dd, 2H)
＜synthesis example 6〉2-ethyl-2-adamantyl-9-tetracyclododecane-4-methyl-4-carboxylicesters synthetic
In the 0.25L autoclave, add DCPD (Dicyclopentadiene (DCPD), Aldrich, 10.2ml, 0.0757mol) and methacrylic acid 2-ethyl-2-adamantane esters (44.3g, 0.18mol), make it 200 ℃ of reactions 12 hours then, adding DCPD (Dicyclopentadiene (DCPD) to the gained reaction solution, Aldrich, 5.1ml, 0.0379mol) afterwards, make it then 200 ℃ of reactions 8 hours.With the reaction product cooling, transfer in the water distilling apparatus, use vacuum pump under the decompression of 1 holder, to distill then, thereby obtain the finished product (productive rate: 27%) at 120 ℃.The exo isomer of this product and the mol ratio of endo isomer (mol%) are 43.7:56.3.
1H-NMR (500MHz, CDCl 3), interior type: δ 6.32 (dd, 1H), 6.20 (dd, 1H), 2.32 (dd, 2H); External form: δ 6.25 (m, 2H), 2.40 (dd, 2H)
＜synthesis example 7〉2-methyl-2-adamantyl-9-tetracyclododecane-4-ethyl-4-carboxylicesters synthetic
In the 0.25L autoclave, add DCPD (Dicyclopentadiene (DCPD), Aldrich, 10.2ml, 0.0757mol) and ethylacrylic acid 2-methyl-2-adamantane esters (44.3g, 0.18mol), make it 210 ℃ of reactions 12 hours then, adding DCPD (Dicyclopentadiene (DCPD) to the gained reaction solution, Aldrich, 5.1ml, 0.0379mol) afterwards, make it then 210 ℃ of reactions 8 hours.With the reaction product cooling, transfer in the water distilling apparatus, use vacuum pump under the decompression of 1 holder, to distill then, thereby obtain the finished product (productive rate: 34%) at 117 ℃.The exo isomer of this product and the mol ratio of endo isomer (mol%) are 50.1:49.9.
1H-NMR (500MHz, CDCl 3), interior type: δ 6.31 (dd, 1H), 6.23 (dd, 1H), 2.30 (dd, 2H); External form: δ 6.27 (m, 2H), 2.39 (dd, 2H)
＜synthesis example 8〉1-adamantyl-9-tetracyclododecane-4-methyl-4-carboxylicesters synthetic
In the 0.25L autoclave, add DCPD (Dicyclopentadiene (DCPD), Aldrich, 10.2ml, 0.0757mol) and methacrylic acid 1-adamantane esters (40.0g, 0.18mol), make it 200 ℃ of reactions 12 hours then, adding DCPD (Dicyclopentadiene (DCPD) to the gained reaction solution, Aldrich, 5.1ml, 0.0379mol) afterwards, make it then 200 ℃ of reactions 8 hours.With the reaction product cooling, transfer in the water distilling apparatus, use vacuum pump under the decompression of 1 holder, to distill then, thereby obtain the finished product (productive rate: 75%) at 100 ℃.The exo isomer of this product and the mol ratio of endo isomer (mol%) are 45.2:54.8.
1H-NMR (500MHz, CDCl 3), interior type: δ 6.34 (dd, 1H), 6.27 (dd, 1H), 2.32 (dd, 2H); External form: δ 6.31 (m, 2H), 2.34 (dd, 2H)
＜contrast synthesis example 1〉norbornylene-2-carboxylate methyl ester synthetic
In the 0.5L autoclave, add DCPD (Dicyclopentadiene (DCPD), Aldrich, 67ml, 0.5mol), methyl acrylate (Aldrich, 94.6ml, 1.05mol) and quinhydrones (2.3g, 0.02mol), make it 200 ℃ of reactions 12 hours then, after the reaction product cooling, transfer in the water distilling apparatus, use vacuum pump under the decompression of 1 holder, to distill then, thereby obtain the finished product (productive rate: 89%) at 50 ℃.The exo isomer of this product and the mol ratio of endo isomer (mol%) are 52.8:47.2.
1H-NMR (500MHz, CDCl 3), interior type: δ 6.17 (dd, 1H), 5.91 (dd, 1H), 3.60 (s, 3H), 3.17 (b, 1H), 2.91 (m, 1H), 2.88 (b, 1H), 1.28 (m, 1H); External form: δ 6.09 (m, 2H), 3.67 (s, 3H), 3.01 (b, 1H), 2.88 (b, 1H), 2.20 (m, 1H), 1.88 (m, 1H), 1.51 (d, 1H), 1.34 (m, 2H)
＜contrast synthesis example 2〉2-adamantyl-5-norbornylene-2-carboxylicesters synthetic
In the 0.25L autoclave, add DCPD (Dicyclopentadiene (DCPD), Aldrich, 10.2ml, 0.0757mol), vinylformic acid 2-adamantane esters (37.1g, 0.18mol) and quinhydrones (0.83g, 0.1mol), make then its 200 ℃ the reaction 12 hours, after the reaction product cooling, transfer in the water distilling apparatus, use vacuum pump under the decompression of 1 holder, to distill then, thereby obtain the finished product (productive rate: 40%) at 120 ℃.The exo isomer of this product and the mol ratio of endo isomer (mol%) are 50.2:49.8.
1H-NMR (500MHz, CDCl 3), interior type: δ 6.22 (dd, 1H), 6.19 (dd, 1H); External form: δ 6.17 (m, 2H)
Synthetic (embodiment 1～10, Comparative Examples 1～2) of norbornylene-ester polymer
＜embodiment 1〉2-methyl-2-adamantyl-5-norbornylene-2-methyl-2-carboxylicesters homopolymer
Nickelous chloride (NiCl to 0.13g (1.0mmol) 2) in add the ethanol of 3ml, make temperature remain under 60 ℃ the situation synthetic 2-methyl-2-adamantyl-5-norbornylene-2-methyl-2-carboxylicesters in the synthesis example 1 of wherein adding 20g (6.73mmol) afterwards, thereby reacting 12 hours.After reaction is finished, the temperature of reactor is reduced to room temperature, the gained reaction solution is added drop-wise in the excessive methanol, thereby forms sedimentary first throw out.First throw out is dissolved in the ethanol of 5ml, deposits second throw out in the excessive methanol thereby afterwards this throw out drips of solution is added to.Leach second throw out, then in vacuum chamber 60 ℃ of dryings 24 hours, thereby obtain 5-norbornylene-2-carboxylate methyl ester homopolymer.By vacuum-drying with the resulting polymers purifying.As the result of present embodiment, the productive rate of resulting polymers is 12g (60%) after measured, and its molecular weight is 35,000 after measured, and its molecular weight distribution is 2.0 after measured.
＜embodiment 2〉2-ethyl-2-adamantyl-5-norbornylene-2-methyl-2-carboxylicesters homopolymer
Except that the synthesis example 2 synthetic 2-ethyls-2-adamantyl-5-norbornylene-2-methyl-2-carboxylicesters that uses 20g (6.47mmol) substitutes 2-methyl-2-adamantyl-5-norbornylene-2-methyl-2-carboxylicesters, carry out polymerization in the mode identical with embodiment 1.Catalyzer and monomer use according to the mol ratio identical with embodiment 1.As the result of present embodiment, the productive rate of resulting polymers is 10g (50%) after measured, and its molecular weight is 22,000 after measured, and its molecular weight distribution is 1.48 after measured.
＜embodiment 3〉2-methyl-2-adamantyl-5-norbornylene-2-ethyl-2-carboxylicesters homopolymer
Except that the synthesis example 3 synthetic 2-methyl-2-adamantyl-5-norbornylene-2-ethyl-2-carboxylicesters that uses 20g (6.47mmol) substitutes 2-methyl-2-adamantyl-5-norbornylene-2-methyl-2-carboxylicesters, carry out polymerization in the mode identical with embodiment 1.Catalyzer and monomer use according to the mol ratio identical with embodiment 5.As the result of present embodiment, the productive rate of resulting polymers is 9.2g (46%) after measured, and its molecular weight is 21,000 after measured, and its molecular weight distribution is 1.72 after measured.
＜embodiment 4〉1-adamantyl-5-norbornylene-2-methyl-2-carboxylicesters homopolymer
Except that the synthesis example 4 synthetic 1-adamantyls-5-norbornylene-2-methyl-2-carboxylicesters that uses 20g (6.99mmol) substitutes 2-methyl-2-adamantyl-5-norbornylene-2-methyl-2-carboxylicesters, carry out polymerization in the mode identical with embodiment 1.Catalyzer and monomer use according to the mol ratio identical with embodiment 1.As the result of present embodiment, the productive rate of resulting polymers is 16g (80%) after measured, and its molecular weight is 26,000 after measured, and its molecular weight distribution is 1.42 after measured.
＜embodiment 5〉2-methyl-2-adamantyl-9-tetracyclododecane-4-methyl-4-carboxylicesters homopolymer
Except that the synthesis example 5 synthetic 2-methyl-2-adamantyl-9-tetracyclododecane-4-methyl-4-carboxylicesters that uses 20g (5.46mmol) substitutes 2-methyl-2-adamantyl-5-norbornylene-2-methyl-2-carboxylicesters, carry out polymerization in the mode identical with embodiment 1.Catalyzer and monomer use according to the mol ratio identical with embodiment 1.As the result of present embodiment, the productive rate of resulting polymers is 15g (81%) after measured, and its molecular weight is 31,500 after measured, and its molecular weight distribution is 1.92 after measured.
＜embodiment 6〉2-ethyl-2-adamantyl-9-tetracyclododecane-4-methyl-4-carboxylicesters homopolymer
Except that the synthesis example 6 synthetic 2-ethyls-2-adamantyl-9-tetracyclododecane-4-methyl-4-carboxylicesters that uses 20g (5.26mmol) substitutes 2-methyl-2-adamantyl-5-norbornylene-2-methyl-2-carboxylicesters, carry out polymerization in the mode identical with embodiment 1.Catalyzer and monomer use according to the mol ratio identical with embodiment 1.As the result of present embodiment, the productive rate of resulting polymers is 9g (45%) after measured, and its molecular weight is 14,000 after measured, and its molecular weight distribution is 1.83 after measured.
＜embodiment 7〉2-methyl-2-adamantyl-9-tetracyclododecane-4-ethyl-4-carboxylicesters homopolymer
Except that the synthesis example 7 synthetic 2-methyl-2-adamantyl-9-tetracyclododecane-4-ethyl-4-carboxylicesters that uses 20g (5.26mmol) substitutes 2-methyl-2-adamantyl-5-norbornylene-2-methyl-2-carboxylicesters, carry out polymerization in the mode identical with embodiment 1.Catalyzer and monomer use according to the mol ratio identical with embodiment 1.As the result of present embodiment, the productive rate of resulting polymers is 12g (60%) after measured, and its molecular weight is 27,000 after measured, and its molecular weight distribution is 1.27 after measured.
＜embodiment 8〉1-adamantyl-9-tetracyclododecane-4-methyl-4-carboxylicesters homopolymer
Except that the synthesis example 8 synthetic 1-adamantyls-9-tetracyclododecane-4-methyl-4-carboxylicesters that uses 20g (5.68mmol) substitutes 2-methyl-2-adamantyl-5-norbornylene-2-methyl-2-carboxylicesters, carry out polymerization in the mode identical with embodiment 1.Catalyzer and monomer use according to the mol ratio identical with embodiment 1.As the result of present embodiment, the productive rate of resulting polymers is 9.5g (48%) after measured, and its molecular weight is 34,000 after measured, and its molecular weight distribution is 1.53 after measured.
＜embodiment 9〉2-methyl-2-adamantyl-5-norbornylene-2-methyl-2-carboxylicesters and 2-ethyl-2-adamantyl-9-tetracyclododecane-4-methyl-4-carboxylate copolymer
Nickelous chloride (NiCl to 1.0mmol 2) the middle ethanol that adds 10ml, afterwards temperature is remained under 60 ℃ the situation to wherein adding the 2-ethyl-2-adamantyl-9-tetracyclododecane-4-methyl-4-carboxylicesters of synthetic 2-methyl-2-adamantyl-5-norbornylene-2-methyl-2-carboxylicesters and synthesis example 5 in the synthesis example 1 with mol ratio 1:1, thereby reacting 15 hours.After reaction is finished, the temperature of reactor is reduced to room temperature, the gained reaction solution is added drop-wise in the excessive methanol, thereby forms sedimentary first throw out.First throw out is dissolved in the ethanol of 5ml, deposits second throw out in the excessive methanol thereby afterwards this throw out drips of solution is added to.Leach second throw out, then in vacuum chamber 60 ℃ of dryings 24 hours, thereby obtain 5-norbornylene-2-carboxylate methyl ester homopolymer.By vacuum-drying with the resulting polymers purifying.As the result of present embodiment, the productive rate of resulting polymers is 62% after measured, and its molecular weight is 42,000 after measured, and its molecular weight distribution is 2.2 after measured.
＜embodiment 10〉1-adamantyl-5-norbornylene-2-methyl-2-carboxylicesters and 2-ethyl-2-adamantyl-9-tetracyclododecane-4-methyl-4-carboxylate copolymer
Except that using synthesis example 4 synthetic 1-adamantyls-5-norbornylene-2-methyl-2-carboxylicesters and synthesis example 6 synthetic 2-ethyls-2-adamantyl-9-tetracyclododecane-4-methyl-4-carboxylicesters, carry out polymerization in the mode identical with embodiment 9.As the result of present embodiment, the productive rate of resulting polymers is 48% after measured, and its molecular weight is 37,600 after measured, and its molecular weight distribution is 2.53 after measured.
＜Comparative Examples 1〉norbornylene-2-carboxylate methyl ester homopolymer
Except that the contrast synthesis example 1 synthetic norbornylene-2-carboxylate methyl ester that uses 50g (0.33mmol) substitutes 2-methyl-2-adamantyl-5-norbornylene-2-methyl-2-carboxylicesters, carry out polymerization in the mode identical with embodiment 1.Catalyzer and monomer use according to the mol ratio identical with embodiment 1.As the result of this Comparative Examples, the productive rate of resulting polymers is 40g (80%) after measured, and its molecular weight is 60,000 after measured, and its molecular weight distribution is 1.7 after measured.
＜Comparative Examples 2〉2-adamantyl-5-norbornylene-2-carboxylicesters homopolymer
Except that the contrast synthesis example 2 synthetic 2-adamantyls-5-norbornylene-2-carboxylicesters that uses 20g (7.3mmol) substitutes 2-methyl-2-adamantyl-5-norbornylene-2-methyl-2-carboxylicesters, carry out polymerization in the mode identical with embodiment 1.Catalyzer and monomer use according to the mol ratio identical with embodiment 1.As the result of this Comparative Examples, the productive rate of resulting polymers is 8.8g (44%) after measured, and its molecular weight is 23,000 after measured, and its molecular weight distribution is 2.1 after measured.
The preparation of film
＜embodiment 11～20, Comparative Examples 3～4 〉
Use each polymer manufacture film of embodiment 1～10 and Comparative Examples 1 and 2.Particularly, each polymkeric substance of embodiment 1～10 and Comparative Examples 1 and 2 is mixed with the organic solvent shown in the table 1 composed as follows, thereby make coating fluid, use spreader (YOSHMITSU YBA-4) that it is cast on the substrate of glass then, drying at room temperature 1 hour, in nitrogen atmosphere 100 ℃ further dry 18 hours, left standstill 10 seconds at-10 ℃ then.Afterwards, use scraper to remove the gained film from this substrate of glass, thus obtain embodiment as shown in table 1 below 11～20 and Comparative Examples 3～4 have uniform thickness, variation in thickness less than each transparent film of 5%.
Table 1
Figure A200780007328D00161
The evaluation of＜character 〉
(1) second-order transition temperature
Use TGA (thermogravimetric analyzer) and DSC (differential scanning calorimeter) to measure the second-order transition temperature of each polymkeric substance of embodiment 1～10 and Comparative Examples 1～2.
The results are shown in the following table 2.
Table 2
Numbering Second-order transition temperature (℃)
Embodiment 1 233
Embodiment 2 215
Embodiment 3 234
Embodiment 4 240
Embodiment 5 230
Embodiment 6 246
Embodiment 7 237
Embodiment 8 225
Embodiment 9 231
Embodiment 10 239
Comparative Examples 1 280
Comparative Examples 2 222
(2) metal tackiness
Metal tackiness for each polymkeric substance of estimating embodiment 1～10 and Comparative Examples 1 and 2 is dissolved in this polymkeric substance in the toluene of 10 weight %, then at the thickness that is being coated with coating 1 μ m on each sheet glass of chromium, aluminium and tungsten pattern.With the form cross cut of this film with the square grid, each square is width 5mm * length 5mm, carries out 180 ° of adhesive tape tests then.As a result, the square of embodiment 1～10 and Comparative Examples 1 and 2 sample separates with the sheet glass that is coated with described pattern.
(3) transmittance
Use turbidometer (NIPPON DENSHOKU 300A) each film of embodiment 11～20 and Comparative Examples 3 and 4 to be measured in the optical absorption intensity of suprabasil vertical incidence light intensity, this substrate and the luminous reflectance intensity of this substrate, determine transmittance according to following equation 1 again at the wavelength place of 400nm～800nm.The results are shown in the following table 3.
Equation 1
l 0 - ( l a + l r ) l 0 = T
Wherein, l 0=in suprabasil vertical incidence light intensity,
l aThe optical absorption intensity of=substrate and
l rThe luminous reflectance intensity of=substrate.
(4) water absorbability
Each film of embodiment 11～20 and Comparative Examples 3 and 4 is cut into the size of 10cm * 10cm, it was placed 24 hours in 25 ℃ water, determine water absorbability according to changes in weight afterwards.The results are shown in the following table 3.
Table 3
Numbering Transmittance (T) Water absorbability (%)
Embodiment 11 0.93 0.037
Embodiment 12 0.97 0.035
Embodiment 13 0.95 0.032
Embodiment 14 0.94 0.034
Embodiment 15 0.93 0.026
Embodiment 16 0.92 0.028
Embodiment 17 0.93 0.025
Embodiment 18 0.92 0.030
Embodiment 19 0.93 0.031
Embodiment 20 0.93 0.027
Comparative Examples 3 0.85 0.022
Comparative Examples 4 0.88 0.041
It is evident that in the above-mentioned evaluation result, have adamantyl as the second-order transition temperature of the substituent norbornylene-ester polymer of large volume more than 200 ℃, thereby demonstrate very high thermostability, therefore be suitable for electronic material, also have the good metal tackiness.
As can be seen, use to have the film that adamantyl is made as the substituent norbornylene-ester polymer of large volume, and do not compare, have the transmittance of further raising with its film of making.And this film has agent of low hygroscopicity, has therefore realized good dimensional stability.

Claims (6)

1. norbornylene-ester polymer:
I) carbon that comprises by following formula 1 expression of described norbornylene-ester polymer adds up to norbornylene-ester cpds repeating unit of 19～80; And
Ii) the transmittance of described norbornylene-ester polymer is more than 0.9, described transmittance is measured in the following manner: with described polymer formation is casting films, use turbidometer to measure this casting films at the wavelength place of 400nm～800nm then, determine transmittance according to following equation 1 again in the optical absorption intensity of suprabasil vertical incidence light intensity, this substrate and the luminous reflectance intensity of this substrate:
Formula 1
Figure A200780007328C00021
Wherein, the R that is same to each other or different to each other 1, R 2And R 3Hydrogen atom, C respectively do for oneself 1～10Straight or branched alkyl or C 5～12Cycloalkyl, R 1, R 2And R 3In at least one be not hydrogen atom, R 4Have and be selected from
Figure A200780007328C00022
With
Figure A200780007328C00023
In structure, wherein, R 5Be hydrogen atom, C 1～10Straight or branched alkyl or C 5～12Cycloalkyl, n is the integer more than 0; With
Equation 1
l 0 - ( l a + l r ) l 0 = T
Wherein, l 0Be at suprabasil vertical incidence light intensity, l aBe the optical absorption intensity of this substrate, l rBe the luminous reflectance intensity of this substrate.
2. norbornylene-ester polymer as claimed in claim 1, the glass transition temperature Tg of described norbornylene-ester polymer are 200 ℃～300 ℃.
3. norbornylene-ester polymer as claimed in claim 1, the number-average molecular weight Mn of described norbornylene-ester polymer are more than 10,000, and molecular weight distribution is 1.0～4.0.
4. optical material, described optical material comprises each described norbornylene-ester polymer in the claim 1～3.
5. optical material as claimed in claim 4, the transmittance of described optical material is more than 0.9, described transmittance is measured in the following manner: use turbidometer to measure described optical material at the wavelength place of 400nm～800nm in the optical absorption intensity of suprabasil vertical incidence light intensity, this substrate and the luminous reflectance intensity of this substrate, determine transmittance according to following equation 1 again:
Equation 1
l 0 - ( l a + l r ) l 0 = T
Wherein, l 0Be at suprabasil vertical incidence light intensity, l aBe the optical absorption intensity of this substrate, l rBe the luminous reflectance intensity of this substrate.
6. optical material as claimed in claim 4, wherein, described optical material is a film.
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