CA1171872A - Cyclic pyrophosphate derivatives, their preparation procedure and the dental filling material composed of them - Google Patents
Cyclic pyrophosphate derivatives, their preparation procedure and the dental filling material composed of themInfo
- Publication number
- CA1171872A CA1171872A CA000367042A CA367042A CA1171872A CA 1171872 A CA1171872 A CA 1171872A CA 000367042 A CA000367042 A CA 000367042A CA 367042 A CA367042 A CA 367042A CA 1171872 A CA1171872 A CA 1171872A
- Authority
- CA
- Canada
- Prior art keywords
- cyclic pyrophosphate
- alkyl
- cyclic
- pyrophosphate according
- alkylene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6578—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and sulfur atoms with or without oxygen atoms, as ring hetero atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/098—Esters of polyphosphoric acids or anhydrides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/6574—Esters of oxyacids of phosphorus
Abstract
ABSTRACT OF THE DISCLOSURE
The disclosure describes compounds of the formula:
The disclosure describes compounds of the formula:
Description
;7.~
This invention relates to cyclic pyrophosphate derivatives and their process of preparation. The invention also relates to a dental filling material mainly composed of these derivatives and to the dental filling technique which makes use of this material.
Many kinds of dental cements are used mostly as ; filling materials. Recently some monomers of methacrylate have also been considered as resin-based filling material.
One of the well known monomers of this type is a compound of the following formula (glycidyl methacrylate derivatives of bisphenol ~; Bis-GMA):
oCH2CHCH2oCoc = CH2 3 y OCH2CHCH2OCOIC CH2 which i8 described in U. S. Patents No. 3,066,112 and No.
3,179,623. In order to make the mixture less viscous for practical use, suitable reactive diluents are added to this monomer, such as methyl methacrylate, ethylene glycol dimeth-acrylate, triethylene glycol dimethacrylate or tetraethylene glycol dimethacrylate. For filling teeth cavities, tertiary amines and peroxides are added to the mixture, which is then cured to serve as an excellent restorative material of higher mechanical properties.
The handling characteristics of this material are not so good, since, without adding a large quantity of diluent Bis-GMA is extremely viscous and sometimes it tends to absorb undesirable amounts of water so that the less cured resin has lower mechanical strength. As a fundamental problem, the rd~
- 1 - ~' 1~7187Z
hardening time between gelatination and complete hardening takes so long that a patient must keep his mouth open until the resin is completely cured.
Since the diluents described above are low mole-cular weight monomers, which penetrate into the pulpal tissues thereby irritating the patient, it would be better to reduce the amount of diluent as much as possible.
The main object of this invention is to produce a new resin monomer which overcomes the above mentioned dis-advantages, and which can be completely polymerized in a shorttime without adding lower molecular weight diluents.
It is another object of this invention to provide an effective synthetic process for preparing the resin monomer.
It is another object of this invention to provide a new dental filling material mainly composed of this monomer and a new dental technique of filling cavities using this material.
The new polymerizable monomers according to this invention consist of cyclic pyrophosphate derivatives of the formula:
R 0- P-O~ A ~
~ ~ O- P- O
~ R2 0 wherein:
A represents a bond directly connecting two phenyl rings to form a biphenyl ring or the moiety selected from the group consisting of (lower) alkylene, aryl substituted (lower) al-kylene, cycloalkylidene, sulfonyl and oxy groups, connecting l.t~7~7;~
the two phenyl rings, Rl represents allyl, acryloyloxy (lower) alkyl or methacryloyl-oxy (lower)alkyl radicals, in which the (lower) alkyl portion can be substituted by halogen atoms R represents hydrogen, halogen, lower alkyl or lower alkoxy, Compounds of the ~ormula (I) may be prepared by the following reactions: wherein A, Rl and R2 have the same meanings as shown above, and X is a halogen atom:
HO ~ A~ OH (II) o R \ R2 X2 P- -~ i ~} O- PX2 ( I I I ) o R \ / R2 o Rl O_ p_ o ~ . ~} O- P- ORl ( IV ) ~ H20/amine ~ A ~ - O- P- OR
O ~ ~ O_ll_ORl (I) ~he reaction mechanism involved in the formation of compound (I) from compound (IV) is believed to be due to a partial hydrolysis of compound (IV) to give an intermediate (V), which reacts with the unreacted portion of compound (IV) in the presence of an amine (dehydrohalogenating agent) to produce the compound (I).
1:17.~l~72 A description of the mechanism is as follows:
Rl O_p_O~ A~ o_p-OR (IV) X X
~I H20 , .
anine ¦~R1 O_P_O{~A~O-P-OR1 (V) OH OH
':
Rl 0- p_O_~ A ~ O- P-OR
O O ( I)+2E~X
R1 o P o~L A~ O_lll_OR1 wherein A represents a bond directly connecting two phenyl rings to form a biphenyl ring, or (lower)alkylene, aryl subs-tituted (lower) alkylene, cycloalkylidene, sulfonyl or oxy groups between the two phenyl rings.
The lower alkylene group includes thoqe having from one to six carbon atoms, such as methylene, ethylene, trime-thylene, propylene, dimethyl methylene, tetramethylene, ethyl-ethylene, 2-methyl trimethylene, pentamethylene, 2-ethyl tri-methylene, 2,2-dimethyl trimethylene, 1,3-dimethyl trimethyl-ene, l-ethyl trimethylene or hexamethylene.
The aryl substituted alkylene group includes the lower , alkylene groups described above, which are substituted by means of phenyl, ~-naphthyl, ~-naphthyl or anthranyl groups. The '71.~372 number of aryl substituents is not strictly limited and can vary.
me aryl group can carry suitable substituents, such as lower alkyl, lower alkoxy and halogen atom, wherein the lower alkyl has from one to six carbon atoms, examples of alkyl substituents include methyl, ethyl propyl, iso. propyl, butyl, tert. butyl, pentyl or hexyl, the lower alkoxy substituents have from one to six carbon atoms, such as methoxy, ethoxy, propoxy, iso-propoxy, butoxy, tert-butoxy, pentyloxy or hexyl-oxy, the halogen atom includes fluorine, chlorine, bromine or iodine.
The cycloalkylidene includes cyclopentylidene and cyclohexylidene.
Rl represents allyl, acryloyloxy (lower) alkyl or methacryloyloxy (lower) alkyl, in which the vinyl group is responsible for the polymerizability of compound (I). The lower alkyl group in Rl is the same as in A. ~his lower alkyl group can be substituted by halogen atoms, such as fluorine, chlorine, bromine or iodine.
R2 is a substituent which can occupy an arbitrary po-sition of the phenyl ring and includes lower alkyl, lower alkoxy and halogen atom, which are the same as described above.
Ihe process for the preparation of compound (I) is as follows:
Compound (II) -~ Compound (III) Under anhydrous condition, compound (II) is reacted with phosphoryl chloride which acts both as a reagent and a solvent. Another suitable solvent can be added to the reac-tion mixture. The reaction temperature is not specially ; defined, but reflux or heating is better for completion of li71.~7z the reaction.
Compound (III) -~ Compound (IV) Under anhydrous condition, an alcohol of formula RlOH
is reacted with compound (III~. The reaction is usually carried out in the presence of solvents, such as methylene chloride or chloroform, which do not hinder the reaction. The reaction temperature is not strictly defined, but mild con-ditions between cooling and room temperature are recommended.
Compound (IV)-~ Compound (I) Ihe reaction involves the intermediate (V) and the hydrolysis is immediately followed by a condensation accom-panied by a removal of hydrogen chloride. For the hydrolysis to take place it is merely necessary to add water to the re-action mixture' the temperature is not critical. Condensa-tion accompanied by removal of hydrogen chloride in the pre-sence of the organic or inorganic base, which is added to the reaction mixture while the hydrolysis is proceeding. The hydrolysed intermediate reacts with the remaining unhydrolysed compound to give compound (I). The type of base which is added is not critical but a tertiary amine, such as trialkyl amine or pyridine, is preferred as an organic base, and a weak base, such as a carbonate, can be used as an inorganic base.
Compound (I) obtained by the process described above , is a polymerizable monomer in which the vinyl group causes the polymerization. The polymerization takes place by means of light, heat or ultra violet light, it may also be carried out in the presence of an initiator and an accelerator. A
peroxide such as benzoic peroxide, may be used as an initiator, while an amine may constitute the accelerator.
Although compound (I) can be used as a dental filling material all by itself, an organic or inorganic filler may be combined with compound (I) to get higher strength. The hardening time of this monomer is so short that a patient does not have to keep his mouth open. ~his monomer is not so viscous so that a diluent need not be combined therewith to lessen pulpal irritation. After curing, this monomer gives the resin excellent physical properties, such as com-pressive strength, hardness and anti-abrasion, so that it is useful and can be applied in various kinds of technical fields, not only as a dental filling material but as a material for industrial use.
The invention is further illustrated by means of the following examples.
A mixture of bis-phenol A (228 g), phosphoryl chloride (320 g) and calcium chloride (50 g) was heated at 150C for 5 hours. After the reaction was over, an excess amount of phos-phoryl chloride was distilled out under reduced pressure to give the following phosphoryl dichloride:
' 0 CH3 0 C12P ~ C ~ 0-1lC12 A solution of the phosphoryl dichloride in methylene chloride (500 ml) was added dropwise at 0C to a solution of
This invention relates to cyclic pyrophosphate derivatives and their process of preparation. The invention also relates to a dental filling material mainly composed of these derivatives and to the dental filling technique which makes use of this material.
Many kinds of dental cements are used mostly as ; filling materials. Recently some monomers of methacrylate have also been considered as resin-based filling material.
One of the well known monomers of this type is a compound of the following formula (glycidyl methacrylate derivatives of bisphenol ~; Bis-GMA):
oCH2CHCH2oCoc = CH2 3 y OCH2CHCH2OCOIC CH2 which i8 described in U. S. Patents No. 3,066,112 and No.
3,179,623. In order to make the mixture less viscous for practical use, suitable reactive diluents are added to this monomer, such as methyl methacrylate, ethylene glycol dimeth-acrylate, triethylene glycol dimethacrylate or tetraethylene glycol dimethacrylate. For filling teeth cavities, tertiary amines and peroxides are added to the mixture, which is then cured to serve as an excellent restorative material of higher mechanical properties.
The handling characteristics of this material are not so good, since, without adding a large quantity of diluent Bis-GMA is extremely viscous and sometimes it tends to absorb undesirable amounts of water so that the less cured resin has lower mechanical strength. As a fundamental problem, the rd~
- 1 - ~' 1~7187Z
hardening time between gelatination and complete hardening takes so long that a patient must keep his mouth open until the resin is completely cured.
Since the diluents described above are low mole-cular weight monomers, which penetrate into the pulpal tissues thereby irritating the patient, it would be better to reduce the amount of diluent as much as possible.
The main object of this invention is to produce a new resin monomer which overcomes the above mentioned dis-advantages, and which can be completely polymerized in a shorttime without adding lower molecular weight diluents.
It is another object of this invention to provide an effective synthetic process for preparing the resin monomer.
It is another object of this invention to provide a new dental filling material mainly composed of this monomer and a new dental technique of filling cavities using this material.
The new polymerizable monomers according to this invention consist of cyclic pyrophosphate derivatives of the formula:
R 0- P-O~ A ~
~ ~ O- P- O
~ R2 0 wherein:
A represents a bond directly connecting two phenyl rings to form a biphenyl ring or the moiety selected from the group consisting of (lower) alkylene, aryl substituted (lower) al-kylene, cycloalkylidene, sulfonyl and oxy groups, connecting l.t~7~7;~
the two phenyl rings, Rl represents allyl, acryloyloxy (lower) alkyl or methacryloyl-oxy (lower)alkyl radicals, in which the (lower) alkyl portion can be substituted by halogen atoms R represents hydrogen, halogen, lower alkyl or lower alkoxy, Compounds of the ~ormula (I) may be prepared by the following reactions: wherein A, Rl and R2 have the same meanings as shown above, and X is a halogen atom:
HO ~ A~ OH (II) o R \ R2 X2 P- -~ i ~} O- PX2 ( I I I ) o R \ / R2 o Rl O_ p_ o ~ . ~} O- P- ORl ( IV ) ~ H20/amine ~ A ~ - O- P- OR
O ~ ~ O_ll_ORl (I) ~he reaction mechanism involved in the formation of compound (I) from compound (IV) is believed to be due to a partial hydrolysis of compound (IV) to give an intermediate (V), which reacts with the unreacted portion of compound (IV) in the presence of an amine (dehydrohalogenating agent) to produce the compound (I).
1:17.~l~72 A description of the mechanism is as follows:
Rl O_p_O~ A~ o_p-OR (IV) X X
~I H20 , .
anine ¦~R1 O_P_O{~A~O-P-OR1 (V) OH OH
':
Rl 0- p_O_~ A ~ O- P-OR
O O ( I)+2E~X
R1 o P o~L A~ O_lll_OR1 wherein A represents a bond directly connecting two phenyl rings to form a biphenyl ring, or (lower)alkylene, aryl subs-tituted (lower) alkylene, cycloalkylidene, sulfonyl or oxy groups between the two phenyl rings.
The lower alkylene group includes thoqe having from one to six carbon atoms, such as methylene, ethylene, trime-thylene, propylene, dimethyl methylene, tetramethylene, ethyl-ethylene, 2-methyl trimethylene, pentamethylene, 2-ethyl tri-methylene, 2,2-dimethyl trimethylene, 1,3-dimethyl trimethyl-ene, l-ethyl trimethylene or hexamethylene.
The aryl substituted alkylene group includes the lower , alkylene groups described above, which are substituted by means of phenyl, ~-naphthyl, ~-naphthyl or anthranyl groups. The '71.~372 number of aryl substituents is not strictly limited and can vary.
me aryl group can carry suitable substituents, such as lower alkyl, lower alkoxy and halogen atom, wherein the lower alkyl has from one to six carbon atoms, examples of alkyl substituents include methyl, ethyl propyl, iso. propyl, butyl, tert. butyl, pentyl or hexyl, the lower alkoxy substituents have from one to six carbon atoms, such as methoxy, ethoxy, propoxy, iso-propoxy, butoxy, tert-butoxy, pentyloxy or hexyl-oxy, the halogen atom includes fluorine, chlorine, bromine or iodine.
The cycloalkylidene includes cyclopentylidene and cyclohexylidene.
Rl represents allyl, acryloyloxy (lower) alkyl or methacryloyloxy (lower) alkyl, in which the vinyl group is responsible for the polymerizability of compound (I). The lower alkyl group in Rl is the same as in A. ~his lower alkyl group can be substituted by halogen atoms, such as fluorine, chlorine, bromine or iodine.
R2 is a substituent which can occupy an arbitrary po-sition of the phenyl ring and includes lower alkyl, lower alkoxy and halogen atom, which are the same as described above.
Ihe process for the preparation of compound (I) is as follows:
Compound (II) -~ Compound (III) Under anhydrous condition, compound (II) is reacted with phosphoryl chloride which acts both as a reagent and a solvent. Another suitable solvent can be added to the reac-tion mixture. The reaction temperature is not specially ; defined, but reflux or heating is better for completion of li71.~7z the reaction.
Compound (III) -~ Compound (IV) Under anhydrous condition, an alcohol of formula RlOH
is reacted with compound (III~. The reaction is usually carried out in the presence of solvents, such as methylene chloride or chloroform, which do not hinder the reaction. The reaction temperature is not strictly defined, but mild con-ditions between cooling and room temperature are recommended.
Compound (IV)-~ Compound (I) Ihe reaction involves the intermediate (V) and the hydrolysis is immediately followed by a condensation accom-panied by a removal of hydrogen chloride. For the hydrolysis to take place it is merely necessary to add water to the re-action mixture' the temperature is not critical. Condensa-tion accompanied by removal of hydrogen chloride in the pre-sence of the organic or inorganic base, which is added to the reaction mixture while the hydrolysis is proceeding. The hydrolysed intermediate reacts with the remaining unhydrolysed compound to give compound (I). The type of base which is added is not critical but a tertiary amine, such as trialkyl amine or pyridine, is preferred as an organic base, and a weak base, such as a carbonate, can be used as an inorganic base.
Compound (I) obtained by the process described above , is a polymerizable monomer in which the vinyl group causes the polymerization. The polymerization takes place by means of light, heat or ultra violet light, it may also be carried out in the presence of an initiator and an accelerator. A
peroxide such as benzoic peroxide, may be used as an initiator, while an amine may constitute the accelerator.
Although compound (I) can be used as a dental filling material all by itself, an organic or inorganic filler may be combined with compound (I) to get higher strength. The hardening time of this monomer is so short that a patient does not have to keep his mouth open. ~his monomer is not so viscous so that a diluent need not be combined therewith to lessen pulpal irritation. After curing, this monomer gives the resin excellent physical properties, such as com-pressive strength, hardness and anti-abrasion, so that it is useful and can be applied in various kinds of technical fields, not only as a dental filling material but as a material for industrial use.
The invention is further illustrated by means of the following examples.
A mixture of bis-phenol A (228 g), phosphoryl chloride (320 g) and calcium chloride (50 g) was heated at 150C for 5 hours. After the reaction was over, an excess amount of phos-phoryl chloride was distilled out under reduced pressure to give the following phosphoryl dichloride:
' 0 CH3 0 C12P ~ C ~ 0-1lC12 A solution of the phosphoryl dichloride in methylene chloride (500 ml) was added dropwise at 0C to a solution of
2-hydroxyethyl methacrylate (260 g) and pyridine (240 g) in methylene chloride (300 ml). The mixture was stirred for 2 hours to give the following phosphoryl chloride:
CH2=CCOOCH2CH20-P-0 ~ C ~ O-P-OCH2CH20COC=CH2 Cl CH3 Cl :
.,, , .'. ' l t'71~37Z
Cold water was then added followed by stirring for another 2 hours. After hydrolysis was completed, the organic layer was washed with 5% hydrochloric acid, a 5% aqueous solu-tion of sodium hydroxide, and then dried. Evaporation of the solvent gave the pyrophosphate (530 g) as a colorless oil:
CH2= CCCH2 CH2 - P- ~3 C ~ O- P- OCH2 CH2 OCOC= CH2 ¦ CH3 O O
; CH2=CCOOCH2CH20-P-O ~ C ~ O-P-OCH2CH20COC=CH2 ~max' cm 2950, 1720, 1630, 1600, 1365, 1295, 980 NMR(CDC13) :
7.14 (ABq, 4Hx4, arom, Protons) 6.10 (bs, lHx4, vinyl Proton) 5.55 ( m, lHx4, vinyl Proton) 4.25 ( m, 4Hx4, -CH2CH2-) 1.90 ( d, 3Hx4, vinyl CH3) 1.60 ( m, 3Hx4, -CH3) The phosphoryl chloride (470 g), obtained by the same procedure as described in EXAMPLE 1, was reacted with 2-hydroxy propyl methacrylate (288 g) and pyridine (240 g), and the mix-ture was treated in the same manner as in EX~MPLE 1 to give the following pyrophosphate (442 g):
CH2=ccoocH2cHo-p-o ~ 1 30-P-0CHCH20coc=~cH2 ¦ 3 CH3 o CH2=CCOOCH2 CHO- p_ o ~3 C ~3 o_ p_ OCHCH2 OCOC=CH~
max' cm 2950, 1720, 1630, 1600, 1370, 1290, 990 NMR(CDC13) : ~
7.14 (ABq, 4Hx4, arom. protons) 6.10 (bs , lHx4, vinyl proton) 5.55 ( m , lHx4, vinyl proton) 4.85 ( m , lHx4, -CH2CHCH3) 4.15 ( m , 2Hx4, -C_2CHCH2) 1.90 ( d , 3Hx4, vinyl CH3) 101.60 ( m , 3Hx4, -CH3) 1.30 ( m , 3Hx4, -CH2CHC_3) EX~MPLE 3
CH2=CCOOCH2CH20-P-0 ~ C ~ O-P-OCH2CH20COC=CH2 Cl CH3 Cl :
.,, , .'. ' l t'71~37Z
Cold water was then added followed by stirring for another 2 hours. After hydrolysis was completed, the organic layer was washed with 5% hydrochloric acid, a 5% aqueous solu-tion of sodium hydroxide, and then dried. Evaporation of the solvent gave the pyrophosphate (530 g) as a colorless oil:
CH2= CCCH2 CH2 - P- ~3 C ~ O- P- OCH2 CH2 OCOC= CH2 ¦ CH3 O O
; CH2=CCOOCH2CH20-P-O ~ C ~ O-P-OCH2CH20COC=CH2 ~max' cm 2950, 1720, 1630, 1600, 1365, 1295, 980 NMR(CDC13) :
7.14 (ABq, 4Hx4, arom, Protons) 6.10 (bs, lHx4, vinyl Proton) 5.55 ( m, lHx4, vinyl Proton) 4.25 ( m, 4Hx4, -CH2CH2-) 1.90 ( d, 3Hx4, vinyl CH3) 1.60 ( m, 3Hx4, -CH3) The phosphoryl chloride (470 g), obtained by the same procedure as described in EXAMPLE 1, was reacted with 2-hydroxy propyl methacrylate (288 g) and pyridine (240 g), and the mix-ture was treated in the same manner as in EX~MPLE 1 to give the following pyrophosphate (442 g):
CH2=ccoocH2cHo-p-o ~ 1 30-P-0CHCH20coc=~cH2 ¦ 3 CH3 o CH2=CCOOCH2 CHO- p_ o ~3 C ~3 o_ p_ OCHCH2 OCOC=CH~
max' cm 2950, 1720, 1630, 1600, 1370, 1290, 990 NMR(CDC13) : ~
7.14 (ABq, 4Hx4, arom. protons) 6.10 (bs , lHx4, vinyl proton) 5.55 ( m , lHx4, vinyl proton) 4.85 ( m , lHx4, -CH2CHCH3) 4.15 ( m , 2Hx4, -C_2CHCH2) 1.90 ( d , 3Hx4, vinyl CH3) 101.60 ( m , 3Hx4, -CH3) 1.30 ( m , 3Hx4, -CH2CHC_3) EX~MPLE 3
3-chloro-4,4'-dihydroxy biphenyl (324 g), phosphoryl chloride (320 g) and calcium chloride (50 g) were reacted in the same manner as described in EXAMPLE 1 to give the following phosphoryl dichloride (550 g):
Ol l O
C12-P-o ~ 0-P-C12 me phosphoryl dichloride was reacted with 2-hydroxy-ethyl acrylate (220 g) and pyridine (240 g), and treated in the same manner as in EXAMPLE 1 to give the pyrophosphate 20(415 g):
'7~i87,~
Cl O l O
CH2=CHCOOCH2CH20-P-O~ O-P-OCH2CH20cocH=cH2 O o CH2=CHCOOCH2CH20-P-0 ~ 11 2 H2 2 O O
Cl IR ~ max' cm 2950, 1720, 1630, 1600, 1365, 1295, 980, 845 ~MRt CDC13) : ~
7.30 ( m , 3HX2, arom. protons) 7.20 (ABq, 4HX2, arom. protons) 6.35 ( m , 3HX4, vinyl protons)
Ol l O
C12-P-o ~ 0-P-C12 me phosphoryl dichloride was reacted with 2-hydroxy-ethyl acrylate (220 g) and pyridine (240 g), and treated in the same manner as in EXAMPLE 1 to give the pyrophosphate 20(415 g):
'7~i87,~
Cl O l O
CH2=CHCOOCH2CH20-P-O~ O-P-OCH2CH20cocH=cH2 O o CH2=CHCOOCH2CH20-P-0 ~ 11 2 H2 2 O O
Cl IR ~ max' cm 2950, 1720, 1630, 1600, 1365, 1295, 980, 845 ~MRt CDC13) : ~
7.30 ( m , 3HX2, arom. protons) 7.20 (ABq, 4HX2, arom. protons) 6.35 ( m , 3HX4, vinyl protons)
4.25 ( m , 4HX4, -CH2CH2-) Bis (4-hydroxyphenyl) phenylmethane ( 276 g ), phos-phoryl chloride (320 g) and calcium chloride (50 g) were reacted in the same manner as described in EXAMPLE 1 to give the following phosphoryl dichloride (503 g):
~ CH~ 0- IPC12 The phosphoryl dichloride was reacted with allyl al-cohol (110 g) and pyridine ( 240 g), and treated in the same manner as in EXAMPLE 1 to give the pyrophosphate (388 g):
ll7l~7æ
o ~ o CH2=CHCH20-P-O~ CH~ O-P-OCH2CH=CH2 O O
CH2=CHCH20-P-0 ~ CH ~ 0-P-OCH2CH=CH2 IR~ -1 0 max' c 3050, 2900, 1630, 1600, 1365, 1295, 980 NMR(CDC13) : ~
7.20 ( m, 13~2, arom. protons)
~ CH~ 0- IPC12 The phosphoryl dichloride was reacted with allyl al-cohol (110 g) and pyridine ( 240 g), and treated in the same manner as in EXAMPLE 1 to give the pyrophosphate (388 g):
ll7l~7æ
o ~ o CH2=CHCH20-P-O~ CH~ O-P-OCH2CH=CH2 O O
CH2=CHCH20-P-0 ~ CH ~ 0-P-OCH2CH=CH2 IR~ -1 0 max' c 3050, 2900, 1630, 1600, 1365, 1295, 980 NMR(CDC13) : ~
7.20 ( m, 13~2, arom. protons)
5.62 ( rn, 2Hx4, vinyl protons) 5.60 ( s, lHx2, -CH) , 4.10 (bs, lHx4, vinyl proton) 3.50 ( t, 2Hx4, -CH2-) Bis (2-hydroxy-5-chlorophenyl) methane (476 g), phos-phoryl chloride (320 g) and calcium chloride (50 g) were re-.' acted in the same manner as described in EXAMPLE 1 to give the following phosphoryl dichloride (680 g):
Cl Cl '. ~ CH
O O
' O=P P=O
. C12 C12 The phosphoryl dichloride was reacted with 2-hydroxy-; ethyl methacrylate (240 g) and pyridine (240 g), and treated ; in the same manner as in EXAMPLE 1 to give the pyrophosphate (710 g):
71~37z Cl Cl ~ CH2 ~
Cl H3 o ¦ ¦ O ICH3 CH2=CCOOCH2CH2O-P-O I 2 2 2 O O
CH2=CCOOCH2CH20-P--0 0-P-OCH2CH20COC=CH2 CH3 ¦ I O 3 ~C~2~
IR '~max' cm 2950, 1720, 1630, 1600, 1365, 1295, 980, 845 NMR ( CDC13) 7.3 ( m, 3~c4, arom. protons)
Cl Cl '. ~ CH
O O
' O=P P=O
. C12 C12 The phosphoryl dichloride was reacted with 2-hydroxy-; ethyl methacrylate (240 g) and pyridine (240 g), and treated ; in the same manner as in EXAMPLE 1 to give the pyrophosphate (710 g):
71~37z Cl Cl ~ CH2 ~
Cl H3 o ¦ ¦ O ICH3 CH2=CCOOCH2CH2O-P-O I 2 2 2 O O
CH2=CCOOCH2CH20-P--0 0-P-OCH2CH20COC=CH2 CH3 ¦ I O 3 ~C~2~
IR '~max' cm 2950, 1720, 1630, 1600, 1365, 1295, 980, 845 NMR ( CDC13) 7.3 ( m, 3~c4, arom. protons)
6.1() (bs, lHx4, vinyl proton) 5.55 ( m, lHx4, vinyl proton) 4.25 ( m, 4Hx4, -CH2CH2- ) 3.80 ( s, 2Hx2, -CH2-) 1.90 ( d, 3~4, vinyl CH3) Bis (4-hydroxyphenyl) cyclohexane ( 260 g ), phosphoryl chloride ( 320 g ) and calcium chloride (50 g) were reacted in the same manner as described in EXAMPLE 1 to give the following phosphoryl dichloride (480 g):
''' O ~ o C12P-o43/ C~O_IIC12 The phosphoryl dichloride was reacted with 2-hydroxy-ethyl methacrylate (240 g) and pyridine ~240 g), and treated in the same manner as in EXAMPLE 1 to give the following pyro-phosphate (445 g):
CH3 O ~ O CH
CH2=CCOOCH2CH2o_p_0 ~ / ~ O-P--OCH2CH2OCOC=CH2 O O
CH2=CCCH2CH2-P--O~ C/ ~ -P-OCH2CH2OCOIC--CH2 CH3 o ~ CH3 IR: ~ , cm max 2900, 1720, 1630, 1600, 1365, 1295, 985 v NMR(CDC13) : ~
''' O ~ o C12P-o43/ C~O_IIC12 The phosphoryl dichloride was reacted with 2-hydroxy-ethyl methacrylate (240 g) and pyridine ~240 g), and treated in the same manner as in EXAMPLE 1 to give the following pyro-phosphate (445 g):
CH3 O ~ O CH
CH2=CCOOCH2CH2o_p_0 ~ / ~ O-P--OCH2CH2OCOC=CH2 O O
CH2=CCCH2CH2-P--O~ C/ ~ -P-OCH2CH2OCOIC--CH2 CH3 o ~ CH3 IR: ~ , cm max 2900, 1720, 1630, 1600, 1365, 1295, 985 v NMR(CDC13) : ~
7~15 (ABq, 4~x4, arom. protons) 6.10 (bs , lHx4, vinyl proton) 5,55 ( m , lHx4, vinyl proton) i 4.25 ( m , 4Hx4, -CH2CH2-) l.90 ( d , 3Hx4, vinyl CH3) 1.40 ( m , 10Hx2, -(CH2)5-) Bis (4-hydroxyphenyl) sulfone (250 g), phosphoryl chloride (320 g) and calcium chloride (50 g) were reacted in the same manner as described in EXAMPLE 1 to give the following phosphoryl dichloride (464 g):
O O
'' C12P-0~S02~3 0-PC12 1.1'7~ 72 The phosphoryl dichloride was reacted with 2-hydroxy-ethyl methacrylate (240 g) and pyridine (240 g), and treated in the same manner as in EXAMPLE 1 to give the pyrophosphate (512 g) CH2=CCOOCH2CH2O-P~0 ~ S2 ~ 3 O-P-OCH2CH2OCOC=CH2 O O
CH2=CcooCH2CH20-P-o ~ 3 so2 ~ 3 0-P-OCH2CH20COCI=CH2 IR ~ max' cm : 2950, 1720, 1630, 1600, 1365, 1330, 1130, 980 NMR(CDC13) : ~
7.30 (ABq, 4Hx4, arom. protons) 6.10 (bs , 1Hx4, vinyl proton) 5.55 ( m , 1Hx4, vinyl proton) 4.25 ( m , 4Hx4, -CH2CH2-) 1.90 ( d , 3Hx4, -CH3) Bis (4-hydroxyphenyl) ether (202 g), phosphoryl chloride (320 g) and calcium chloride (50 g) were reacted in the same manner as described in EXAMPLE 1 to give the following phosphoryl dichloride (416 g):
O ' O
C12ll-O ~ O ~ o-llcl2 me phosphoryl dichloride was reacted with allyl al-cohol (110 g) and pyridine (240 g), and treated in the same manner as in EXAMPLE 1 to give the following pyrophosphate (308 g):
li71872 ., o o CH2=CH-CH20-P--0 ~ o ~ O-P-OCH2CH-CH2 ,. o o CH2=CH-CH20-P-O ~ O ~ O-P-CH2CH=CH2 - o IR ~max' cm 2900, 1630, 1600, 1365, 1295, 1100, 980 NMR(CDC12) :
7.10 (ABq, 4Hx4, arom. protons) 5.60 ( m , 2Hx4, vinyl protons) 4.10 (bs , lHx4, vinyl proton) 3.50 ( t , 2Hx4, -CH2-) 4,4-dihydroxy biphenyl (29 g), phosphoryl chloride (32 g) and calcium chloride (5 g) were reacted in the same manner as described in EXAMPLE 1 to give the following phos-phoryl dichloride (50 g):
O o C12P-0~3~o_11C12 The phosphoryl dichloride was reacted with 2-chloro-3-hydroxypropyl methacrylate (33 g) and pyridine (24 g), and treated in the same manner as in EXAMPLE 1 to give the `.pyrophosphate (25.5 g):
~ CH Cl 0 0 Cl CH
; 1 3 1 11 ~ ~ 11 1 1 3 ' CH2=CCOOCH2CHCH20-P- ~ ~ O-P-OCH2CHCH20COC=CH2 O O
cH2=ccoocH2cHcH20_P-o ~ 3 ~ o_P-ocH2cHcH2ococ=cH2 CH3 Cl 0 o Cl CH3 -- 1~7~872 max' c 2950, 1720, 1630, 1600, 1370, 1160, 1000, 760 NMR(CDC13) : ~
7.2 (ABq, 4Hx4, arom. protons) 6.10 (bs , 1Hx4, vinyl proton) 5.55 ( m , lHx4, vinyl proton) 4.20 ( m, 4Hx4, -CH2-CH(Cl)-CH2) 3.65 ( m , lHx4, -CH2CH(Cl)CH2-) 1.90 ( d , 3HX4, vinyl CH3) EX~MPLE FOR USE
A fused quartz powder was finely divided in a ball-mill to a particle size under 200 mesh.
To a solution of sodium hydroxide (pH 9.0 ~ 9.8), 0.5 wt% of ~-methacryloxypropyl trimethoxy silane and the quartz powder were added and the mixture was well mixed with stirring to give a mushy paste, which was then dried at 130C to give a silane coupled quartz powder.
The pyrophosphate (70 wt%) which was prepared by the procedure set forth in EXAMPLE 1 was combined with ethylene glycol dimethacrylate (30 wt%) to give a resin binder. The binder (20 wt%) and the silane coupled quartz powder (80 wt%) were well mixed to provide a paste.
The paste was divided into two parts, one of which was mixed with 0.6 wt% of N,N'-dimethyl-p-toluidine to give a uniform dispersion, and to the other there was added 0.8 wt%
of benzoyl peroxide. Each equal amounts of the two disper-sions were mixed and scoured to provide the composite resin.
The handling characteristics and physical properties were - examined.
' 30 The results are shown in the following table:
1.~7187;i~
Examinatlon test ( ) Result *( IV) Gel time (min.) 2.5 0.35 Hardening time (min.) 4.5 0.45 Diametral tensile strength (MPa) 50.1 2.9 Compressive strength (MPa) 314.3 18.6 Transverse strength (MPa) ( ) 106.4 5.0 Modulus of elasticity (MPa)xl0 () 214.3 5.1 Thermal dimensional change (cm/cm/C)xlO 6 36.2 0.1 Rockwell hardness (HRH) 114 0.5 Knoop hardness (50 g, 5 sec.) 86 3 ' Water sorption (mg/cm2) 0.41 0.05 r *(I) According to American Dental Association Specification - No. 27.
*(II) According to International Organization for Standard-ization ISO-4049.
*(III) Calculated according to Japanese Indu~trial Standard JIS K-6705.
*(IV) Estimated ~tandard deviation of 5 test pieces.
O O
'' C12P-0~S02~3 0-PC12 1.1'7~ 72 The phosphoryl dichloride was reacted with 2-hydroxy-ethyl methacrylate (240 g) and pyridine (240 g), and treated in the same manner as in EXAMPLE 1 to give the pyrophosphate (512 g) CH2=CCOOCH2CH2O-P~0 ~ S2 ~ 3 O-P-OCH2CH2OCOC=CH2 O O
CH2=CcooCH2CH20-P-o ~ 3 so2 ~ 3 0-P-OCH2CH20COCI=CH2 IR ~ max' cm : 2950, 1720, 1630, 1600, 1365, 1330, 1130, 980 NMR(CDC13) : ~
7.30 (ABq, 4Hx4, arom. protons) 6.10 (bs , 1Hx4, vinyl proton) 5.55 ( m , 1Hx4, vinyl proton) 4.25 ( m , 4Hx4, -CH2CH2-) 1.90 ( d , 3Hx4, -CH3) Bis (4-hydroxyphenyl) ether (202 g), phosphoryl chloride (320 g) and calcium chloride (50 g) were reacted in the same manner as described in EXAMPLE 1 to give the following phosphoryl dichloride (416 g):
O ' O
C12ll-O ~ O ~ o-llcl2 me phosphoryl dichloride was reacted with allyl al-cohol (110 g) and pyridine (240 g), and treated in the same manner as in EXAMPLE 1 to give the following pyrophosphate (308 g):
li71872 ., o o CH2=CH-CH20-P--0 ~ o ~ O-P-OCH2CH-CH2 ,. o o CH2=CH-CH20-P-O ~ O ~ O-P-CH2CH=CH2 - o IR ~max' cm 2900, 1630, 1600, 1365, 1295, 1100, 980 NMR(CDC12) :
7.10 (ABq, 4Hx4, arom. protons) 5.60 ( m , 2Hx4, vinyl protons) 4.10 (bs , lHx4, vinyl proton) 3.50 ( t , 2Hx4, -CH2-) 4,4-dihydroxy biphenyl (29 g), phosphoryl chloride (32 g) and calcium chloride (5 g) were reacted in the same manner as described in EXAMPLE 1 to give the following phos-phoryl dichloride (50 g):
O o C12P-0~3~o_11C12 The phosphoryl dichloride was reacted with 2-chloro-3-hydroxypropyl methacrylate (33 g) and pyridine (24 g), and treated in the same manner as in EXAMPLE 1 to give the `.pyrophosphate (25.5 g):
~ CH Cl 0 0 Cl CH
; 1 3 1 11 ~ ~ 11 1 1 3 ' CH2=CCOOCH2CHCH20-P- ~ ~ O-P-OCH2CHCH20COC=CH2 O O
cH2=ccoocH2cHcH20_P-o ~ 3 ~ o_P-ocH2cHcH2ococ=cH2 CH3 Cl 0 o Cl CH3 -- 1~7~872 max' c 2950, 1720, 1630, 1600, 1370, 1160, 1000, 760 NMR(CDC13) : ~
7.2 (ABq, 4Hx4, arom. protons) 6.10 (bs , 1Hx4, vinyl proton) 5.55 ( m , lHx4, vinyl proton) 4.20 ( m, 4Hx4, -CH2-CH(Cl)-CH2) 3.65 ( m , lHx4, -CH2CH(Cl)CH2-) 1.90 ( d , 3HX4, vinyl CH3) EX~MPLE FOR USE
A fused quartz powder was finely divided in a ball-mill to a particle size under 200 mesh.
To a solution of sodium hydroxide (pH 9.0 ~ 9.8), 0.5 wt% of ~-methacryloxypropyl trimethoxy silane and the quartz powder were added and the mixture was well mixed with stirring to give a mushy paste, which was then dried at 130C to give a silane coupled quartz powder.
The pyrophosphate (70 wt%) which was prepared by the procedure set forth in EXAMPLE 1 was combined with ethylene glycol dimethacrylate (30 wt%) to give a resin binder. The binder (20 wt%) and the silane coupled quartz powder (80 wt%) were well mixed to provide a paste.
The paste was divided into two parts, one of which was mixed with 0.6 wt% of N,N'-dimethyl-p-toluidine to give a uniform dispersion, and to the other there was added 0.8 wt%
of benzoyl peroxide. Each equal amounts of the two disper-sions were mixed and scoured to provide the composite resin.
The handling characteristics and physical properties were - examined.
' 30 The results are shown in the following table:
1.~7187;i~
Examinatlon test ( ) Result *( IV) Gel time (min.) 2.5 0.35 Hardening time (min.) 4.5 0.45 Diametral tensile strength (MPa) 50.1 2.9 Compressive strength (MPa) 314.3 18.6 Transverse strength (MPa) ( ) 106.4 5.0 Modulus of elasticity (MPa)xl0 () 214.3 5.1 Thermal dimensional change (cm/cm/C)xlO 6 36.2 0.1 Rockwell hardness (HRH) 114 0.5 Knoop hardness (50 g, 5 sec.) 86 3 ' Water sorption (mg/cm2) 0.41 0.05 r *(I) According to American Dental Association Specification - No. 27.
*(II) According to International Organization for Standard-ization ISO-4049.
*(III) Calculated according to Japanese Indu~trial Standard JIS K-6705.
*(IV) Estimated ~tandard deviation of 5 test pieces.
Claims (16)
1. Cyclic pyrophosphate derivatives of the formula:
wherein:
A represents a bond directly connecting two phenyl rings to form a biphenyl ring or the moiety selected from the group consisting of (lower) alkylene, aryl substituted (lower) alkylene, cycloalkylidene, sulfonyl and oxy groups, R1 represents allyl, acryloyloxy (lower) alkyl or methacryloyloxy (lower) alkyl radicals, in which the (lower) alkyl portion can be substituted by halogen atoms;
R2 represents hydrogen, halogen, lower alkyl or lower alkoxy.
wherein:
A represents a bond directly connecting two phenyl rings to form a biphenyl ring or the moiety selected from the group consisting of (lower) alkylene, aryl substituted (lower) alkylene, cycloalkylidene, sulfonyl and oxy groups, R1 represents allyl, acryloyloxy (lower) alkyl or methacryloyloxy (lower) alkyl radicals, in which the (lower) alkyl portion can be substituted by halogen atoms;
R2 represents hydrogen, halogen, lower alkyl or lower alkoxy.
2. Cyclic pyrophosphate according to claim 1 wherein A
represents a bond directly connecting to form a biphenyl ring.
represents a bond directly connecting to form a biphenyl ring.
3. Cyclic pyrophosphate according to claim 1 wherein A
is dimethyl methylene.
is dimethyl methylene.
4. Cyclic pyrophosphate according to claim 1 wherein A
is phenyl methylene.
is phenyl methylene.
5. Cyclic pyrophosphate according to claim 1 wherein A
is sulfonyl.
is sulfonyl.
6. Cyclic pyrophosphate according to claim 1 wherein A
is oxy.
is oxy.
7. Cyclic pyrophosphate according to claim 1 wherein A
is cyclohexylidene.
is cyclohexylidene.
8. Cyclic pyrophosphate according to claim 1 wherein every R is a hydrogen atom.
9 Cyclic pyrophosphate according to claim 1 wherein two R are halogen atoms.
10. Cyclic pyrophosphate according to claim 1 wherein each R is halogen atom.
11. Cyclic pyrophosphate according to claim 8, 9 or 10 wherein R1 is allyl.
12. Cyclic pyrophosphate according to claim 8, 9 or 10 wherein R1 is 2-methacryloyloxy ethyl.
13. Cyclic pyrophosphate according to claim 8, 9 or 10 wherein R1 is 1-methyl-2-methacryloyloxy ethyl.
14. Cyclic pyrophosphate according to claim 8, 9 or 10 wherein R1 is 2-halo-3-methacryloyloxy ethyl.
15. Cyclic pyrophosphate according to claim 8, 9 or 10 wherein R1 is acryloyloxy ethyl.
16. Process for the preparation of cyclic pyrophosphate derivatives which comprises reacting a phenol derivative of the formula:
wherein:
.
A represents a bond directly connecting two phenyl rings to form a biphenyl ring or the moiety selected from the group consisting of (lower) alkylene, aryl substituted (lower) alkylene, cycloalkylidene, sulfonyl and oxy groups;
R2 represents hydrogen, halogen, lower alkyl or lower alkoxy with phosphoryl halide to give the phosphoryl di-halide derivative of the formula:
wherein A and R2 are the same as above, X is a halogen atom, adding an alcohol derivative of the formula, wherein:
R1 represents allyl, acryloyloxy (lower) alkyl or methacryloyloxy (lower) alkyl, in which the (lower) alkyl por-tion can be substituted by halogen atoms, to said phosphoryl dihalide, to give the phosphoryl halide derivative of the formula:
wherein A, R1, R2 and X are the same as defined above, which is then hydrolysed in the presence of amines to give the cyclic pyrophosphate derivative of the following formula:
wherein A, R1 and R2 are the same as defined above.
wherein:
.
A represents a bond directly connecting two phenyl rings to form a biphenyl ring or the moiety selected from the group consisting of (lower) alkylene, aryl substituted (lower) alkylene, cycloalkylidene, sulfonyl and oxy groups;
R2 represents hydrogen, halogen, lower alkyl or lower alkoxy with phosphoryl halide to give the phosphoryl di-halide derivative of the formula:
wherein A and R2 are the same as above, X is a halogen atom, adding an alcohol derivative of the formula, wherein:
R1 represents allyl, acryloyloxy (lower) alkyl or methacryloyloxy (lower) alkyl, in which the (lower) alkyl por-tion can be substituted by halogen atoms, to said phosphoryl dihalide, to give the phosphoryl halide derivative of the formula:
wherein A, R1, R2 and X are the same as defined above, which is then hydrolysed in the presence of amines to give the cyclic pyrophosphate derivative of the following formula:
wherein A, R1 and R2 are the same as defined above.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP114995/1980 | 1980-08-20 | ||
| JP55114995A JPS5828878B2 (en) | 1980-08-20 | 1980-08-20 | Cyclic pyrophosphate derivative |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1171872A true CA1171872A (en) | 1984-07-31 |
Family
ID=14651698
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000367042A Expired CA1171872A (en) | 1980-08-20 | 1980-12-17 | Cyclic pyrophosphate derivatives, their preparation procedure and the dental filling material composed of them |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US4404150A (en) |
| JP (1) | JPS5828878B2 (en) |
| AU (1) | AU542619B2 (en) |
| CA (1) | CA1171872A (en) |
| DE (1) | DE3048410A1 (en) |
| GB (1) | GB2082184B (en) |
Families Citing this family (36)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5828878B2 (en) * | 1980-08-20 | 1983-06-18 | 三金工業株式会社 | Cyclic pyrophosphate derivative |
| US4929746A (en) * | 1981-02-13 | 1990-05-29 | Minnesota Mining And Manufacturing Company | Dentin and enamel adhesive |
| JPS59155592A (en) * | 1983-02-24 | 1984-09-04 | Nippon Piston Ring Co Ltd | Rotor for rotary hydraulic pump |
| US4515733A (en) * | 1983-11-07 | 1985-05-07 | The B. F. Goodrich Co. | Method for making 1,3,5,2,4,6-trioxatriphosphorinanes |
| US4503169A (en) * | 1984-04-19 | 1985-03-05 | Minnesota Mining And Manufacturing Company | Radiopaque, low visual opacity dental composites containing non-vitreous microparticles |
| US4719149A (en) * | 1986-02-28 | 1988-01-12 | Minnesota Mining And Manufacturing Company | Method for priming hard tissue |
| JPS62191449U (en) * | 1986-05-28 | 1987-12-05 | ||
| US5525648A (en) * | 1991-12-31 | 1996-06-11 | Minnesota Mining And Manufacturing Company | Method for adhering to hard tissue |
| FR2710256B1 (en) * | 1993-09-24 | 1997-08-01 | Gilles Billet | Dental prosthesis with composite support shell and resin coating, piece of prepreg fabric, method and machine for manufacturing this prosthesis. |
| WO2001030307A1 (en) | 1999-10-28 | 2001-05-03 | 3M Innovative Properties Company | Dental materials with nano-sized silica particles |
| US6376590B2 (en) | 1999-10-28 | 2002-04-23 | 3M Innovative Properties Company | Zirconia sol, process of making and composite material |
| US6387981B1 (en) | 1999-10-28 | 2002-05-14 | 3M Innovative Properties Company | Radiopaque dental materials with nano-sized particles |
| US6730156B1 (en) | 1999-10-28 | 2004-05-04 | 3M Innovative Properties Company | Clustered particle dental fillers |
| US6572693B1 (en) | 1999-10-28 | 2003-06-03 | 3M Innovative Properties Company | Aesthetic dental materials |
| US6444725B1 (en) | 2000-01-21 | 2002-09-03 | 3M Innovative Properties Company | Color-changing dental compositions |
| US6528555B1 (en) | 2000-10-12 | 2003-03-04 | 3M Innovative Properties Company | Adhesive for use in the oral environment having color-changing capabilities |
| US6613812B2 (en) | 2001-01-03 | 2003-09-02 | 3M Innovative Properties Company | Dental material including fatty acid, dimer thereof, or trimer thereof |
| FR2828206B1 (en) * | 2001-08-03 | 2004-09-24 | Centre Nat Rech Scient | USE OF LYSYL OXIDASE INHIBITORS FOR CELL CULTURE AND TISSUE ENGINEERING |
| CN1319507C (en) | 2002-01-31 | 2007-06-06 | 3M创新有限公司 | Dental pastes, dental articles, and methods |
| US7084115B2 (en) | 2002-04-29 | 2006-08-01 | Oxyplus, Inc. | Inositol pyrophosphates, and methods of use thereof |
| US20040072801A1 (en) * | 2002-06-14 | 2004-04-15 | Nicolau Yves Claude | Sterols bearing pendant allosteric effectors of hemoglobin, and uses thereof |
| US7091259B2 (en) * | 2002-07-03 | 2006-08-15 | 3M Innovative Properties Company | Dental fillers, pastes, and compositions prepared therefrom |
| US6984261B2 (en) | 2003-02-05 | 2006-01-10 | 3M Innovative Properties Company | Use of ceramics in dental and orthodontic applications |
| US7553670B2 (en) * | 2004-04-28 | 2009-06-30 | 3M Innovative Properties Company | Method for monitoring a polymerization in a three-dimensional sample |
| US20060106000A1 (en) * | 2004-07-06 | 2006-05-18 | Claude Nicolau | Use of inositol-tripyrophosphate in treating tumors and diseases |
| US7745423B2 (en) * | 2004-07-06 | 2010-06-29 | NormOxys, Inc | Calcium/sodium salt of inositol tripyrophosphate as an allosteric effector of hemoglobin |
| US20060258626A1 (en) * | 2004-07-06 | 2006-11-16 | Claude Nicolau | Use of inositol-tripyrophosphate in treating tumors and diseases |
| US20070135389A1 (en) * | 2004-07-06 | 2007-06-14 | Claude Nicolau | Tumor eradication by inositol-tripyrophosphate |
| EP2114349B1 (en) | 2006-12-28 | 2016-09-14 | 3M Innovative Properties Company | Dental filler and methods |
| CN101784193A (en) * | 2007-05-01 | 2010-07-21 | 诺尔姆奥克西斯公司 | erythropoietin complementation or replacement |
| DE102007026395A1 (en) | 2007-06-06 | 2008-12-11 | Wilfried Aichhorn | Jasper powder, shell powder and coral powder as a dye in denture materials and dental prostheses and corresponding dental prosthesis formed thereby |
| US9402697B2 (en) | 2012-04-19 | 2016-08-02 | Research Triangle Institute | Modification of ceramic surfaces |
| JP6656146B2 (en) | 2013-10-04 | 2020-03-04 | スリーエム イノベイティブ プロパティズ カンパニー | Dental mill blank |
| US10350297B2 (en) | 2014-10-31 | 2019-07-16 | 3M Innovative Properties Company | Dental materials and methods |
| WO2016069290A1 (en) | 2014-10-31 | 2016-05-06 | 3M Innovative Properties Company | Dental materials and methods |
| EP3265049A1 (en) | 2015-03-05 | 2018-01-10 | 3M Innovative Properties Company | Composite material having ceramic fibers |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3476699A (en) * | 1961-12-18 | 1969-11-04 | Argus Chem | Polyvinyl chloride and olefin polymer compositions having improved resistance to deterioration comprising an organic phosphite ester having at least one aromatic polycarbocyclic group |
| JPS5367740A (en) * | 1976-11-29 | 1978-06-16 | Kuraray Co Ltd | Adhesives for hard tissue of human body |
| JPS5828878B2 (en) * | 1980-08-20 | 1983-06-18 | 三金工業株式会社 | Cyclic pyrophosphate derivative |
-
1980
- 1980-08-20 JP JP55114995A patent/JPS5828878B2/en not_active Expired
- 1980-11-20 AU AU64567/80A patent/AU542619B2/en not_active Ceased
- 1980-12-17 CA CA000367042A patent/CA1171872A/en not_active Expired
- 1980-12-22 DE DE19803048410 patent/DE3048410A1/en active Granted
-
1981
- 1981-02-05 US US06/231,914 patent/US4404150A/en not_active Expired - Fee Related
- 1981-02-19 GB GB8105213A patent/GB2082184B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5828878B2 (en) | 1983-06-18 |
| AU542619B2 (en) | 1985-02-28 |
| DE3048410C2 (en) | 1989-01-12 |
| US4404150A (en) | 1983-09-13 |
| GB2082184A (en) | 1982-03-03 |
| GB2082184B (en) | 1983-09-14 |
| JPS5738791A (en) | 1982-03-03 |
| AU6456780A (en) | 1982-02-25 |
| DE3048410A1 (en) | 1982-04-01 |
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