CN1956947A - Benzylformamidine compounds and plastic products containing the benzylformamidine compounds as ultraviolet light absorbers - Google Patents
Benzylformamidine compounds and plastic products containing the benzylformamidine compounds as ultraviolet light absorbers Download PDFInfo
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- C07C257/10—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines with replacement of the other oxygen atom of the carboxyl group by nitrogen atoms, e.g. amidines
- C07C257/12—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines with replacement of the other oxygen atom of the carboxyl group by nitrogen atoms, e.g. amidines having carbon atoms of amidino groups bound to hydrogen atoms
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- C07C257/10—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines with replacement of the other oxygen atom of the carboxyl group by nitrogen atoms, e.g. amidines
- C07C257/18—Compounds containing carboxyl groups, the doubly-bound oxygen atom of a carboxyl group being replaced by a doubly-bound nitrogen atom, this nitrogen atom not being further bound to an oxygen atom, e.g. imino-ethers, amidines with replacement of the other oxygen atom of the carboxyl group by nitrogen atoms, e.g. amidines having carbon atoms of amidino groups bound to carbon atoms of six-membered aromatic rings
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Abstract
Disclosed herein is a benzylformamidine compound having high ultraviolet light absorption and superior thermal stability that can be suitably used as an ultraviolet light absorber for plastic products which undergo high-temperature treatment or require superior thermal stability. Further disclosed is a plastic product containing the benzylformamidine compound as an ultraviolet light absorber.
Description
Technical field
The present invention relates to can be as benzyl carbonamidine (benzylformamidine) compound of UV light absorber.More specifically, the present invention relates to have the benzyl formamidine compound of high UV absorbing properties and excellent heat stability, this compound can be used as the multiple UV light absorber that stands pyroprocessing or need the plastics of excellent heat stability, the invention still further relates to and contains the plastics of this benzyl formamidine compound as UV light absorber.
Background technology
Usually, generally recognize, be exposed to ultraviolet ray and the photodegradation that causes, can make many synthetical resin products, natural resin product and polymerisable polymerization product (hereinafter, be referred to as " plastics ") physical deterioration, the wearing quality of plastics is degenerated rapidly.Particularly, the photodegradation meeting that produces in the plastics is brought out product variable color and/or decolouring and can be made product be subjected to the influence of external action easily.In order to address the above problem, in the manufacturing processed of multiple plastics, add UV light absorber.
Known have a multiple compound relevant with UV light absorber.As prior art related to the present invention, U.S. Pat 4,021,471 disclose by the carbonamidine of formula 1 expression as UV light absorber:
Formula 1
R wherein
1Be selected from C
1-5Alkyl, B are selected from H, OH, OH, Cl and methoxyl group, R
2Be selected from C
1-9Alkyl and phenyl, A are selected from hydrogen, ethoxycarbonyl, butoxy carbonyl, methoxyl group, ethyl, dimethylamino and chlorine, and D is selected from H, OCH
3And Cl.
Because it has good photostabilization, the UV light absorber that therefore has structure shown in the formula 1 can be used to make multiple synthetical resin products and polymerisable polymerization product effectively.Yet, because most of UV light absorber (comprising the UV light absorber with structure shown in the formula 1) can not show the thermostability of making us abundant satisfaction, therefore, they are standing pyroprocessing or are needing the application in the plastics of excellent heat stability to be subjected to considerable restraint.
Summary of the invention
In view of the above, consider the fact that most of plastics will at high temperature be handled, need not only have high UV absorbing properties strongly but also have the UV light absorber of excellent heat stability.In order to address that need, the inventor has carried out broad research and has had the UV light absorber of high UV absorbing properties and excellent heat stability with exploitation, and has realized the present invention thus.
Thus, the purpose of this invention is to provide the benzyl formamidine compound with high UV absorbing properties and excellent heat stability, this compound is suitable as the multiple UV light absorber that stands pyroprocessing or need the plastics of excellent heat stability.
Another object of the present invention provides and contains the plastics of this benzyl formamidine compound as UV light absorber.
To achieve these goals, according to an aspect of the present invention, provide benzyl formamidine compound by following formula 2 expressions:
Formula 2
Wherein, R
1And R
2Be selected from hydrogen, C independently of one another
1-9Alkyl and C
1-4Carbalkoxy, L
1And L
3Be selected from hydrogen and C independently of one another
1-4Alkyl, L
2Be selected from H and OH.
The conventional formamidine compound of cotype 1 is compared, and the benzyl formamidine compound that is used as the formula 2 of UV light absorber shows good thermostability and high UV absorbing properties.In view of the above, the benzyl formamidine compound of formula 2 can will stand pyroprocessing or need in the manufacturing of plastic prod of excellent heat stability aptly as UV light absorber.
According to a further aspect of the invention, a kind of plastics are provided, and the benzyl formamidine compound of adding formula 2 makes as UV light absorber in the process of the plastic raw materials of these plastics by being selected from synthetic resins, natural resin and polymerisable polymkeric substance at molding.
Because the benzyl formamidine compound of formula 2 has excellent heat stability and high UV absorbing properties, therefore the benzyl formamidine compound is applied to make the plastics that stand pyroprocessing as UV light absorber, make plastics have high UV absorbing properties, strengthened the wearing quality of plastics thus.
Description of drawings
According to the detailed description below in conjunction with accompanying drawing, above-mentioned and other purpose, feature and other advantage of the present invention will more be expressly understood, wherein:
Fig. 1～4 are respectively the compounds of preparation in the embodiment of the invention 1～4
1H-NMR spectrum (CDCl
3, 200MHz);
Fig. 5 is the chart of the benzyl formamidine compound more of the present invention and the absorption of UV of the formamidine compound of routine; With
Fig. 6 is the chart of the benzyl formamidine compound more of the present invention and the thermostability of the formamidine compound of routine.
Embodiment
To more at large illustrate benzyl formamidine compound of the present invention now.
The invention provides can be as the benzyl formamidine compound of UV light absorber, and it is represented by following formula 2:
Formula 2
Wherein, R
1And R
2Be selected from hydrogen, C independently of one another
1-9Alkyl and C
1-4Carbalkoxy, L
1And L
3Be selected from hydrogen and C independently of one another
1-4Alkyl, L
2Be selected from H and OH.
In the benzyl formamidine compound that can represent by formula 2, the compound (R in formula 2 of preferred following formula 3
1Be ethoxycarbonyl):
Formula 3
R wherein
2Be selected from hydrogen, C
1-9Alkyl and C
1-4Carbalkoxy, L
1And L
3Be selected from hydrogen and C independently of one another
1-4Alkyl, L
2Be selected from H and OH.
In the compound that can represent by formula 3, the benzyl formamidine compound (R in formula 3 of preferred following formula 4～6
2Be respectively hydrogen, ethoxycarbonyl and butoxy carbonyl):
Formula 4
L wherein
1And L
3Be selected from hydrogen and C independently of one another
1-4Alkyl, L
2Be selected from H and OH;
Formula 5
L wherein
1, L
2And L
3Suc as formula in 4 define; With
Formula 6
L wherein
1, L
2And L
3Suc as formula in 4 define.
In having the benzyl formamidine compound of structure shown in the formula 4, particularly preferred compound is the N-3 of following formula 7,5-two-tertiary butyl-4-hydroxy benzyl-N '-4-carbethoxy phenyl-N-phenyl formamidine (L in formula 4
1And L
3Be the tertiary butyl, L
2Be OH):
Formula 7
In having the benzyl formamidine compound of structure shown in the formula 5, preferred compound is the N of following formula 8, N '-two (4-carbethoxy phenyl)-N '-benzyl carbonamidine (L in the formula 5
1, L
2And L
3Be hydrogen) and the N of following formula 9, N '-two (4-ethoxy carbonyl phenyl)-N-3,5-di-tert-butyl-4-hydroxyl benzyl carbonamidine (L in the formula 5
1And L
3Be the tertiary butyl, and L
2Be OH):
Formula 8
Formula 9
In having the benzyl formamidine compound of structure shown in the formula 6, particularly preferred compound is N-4-butoxy carbonyl phenyl-N '-4-carbethoxy phenyl-N-3 of following formula 10,5-two-tertiary butyl-4-hydroxy benzyl carbonamidine (L in the formula 6
1And L
3Be the tertiary butyl, L
2Be OH):
Formula 10
Owing to compare with the formamidine compound of routine, benzyl formamidine compound according to the present invention has showed high UV absorbing properties and good thermostability, therefore can stand pyroprocessing or need the synthetical resin products of excellent heat stability and the manufacturing of polymeric articles in them suitably as UV light absorber.
According to following response hierarchy, can easily make the benzyl formamidine compound of formula 2 of the present invention:
Reaction 1
Reaction 2
Reaction 3
In reaction 1～3, R
1, R
2, L
1, L
2And L
3Suc as formula in 2 define.
Owing to compare with the formamidine compound of routine, therefore benzyl formamidine compound of the present invention has showed good thermostability and high UV absorbing properties, can stand pyroprocessing or need in the manufacturing of plastics of excellent heat stability them suitably as UV light absorber.
In the plastics that undertaken by the plastic raw materials that is selected from synthetic resins, natural resin and polymerizable polymkeric substance are made, benzyl formamidine compound of the present invention can be added as UV light absorber.Particularly and since the benzyl formamidine compound with as the urethane and the polyvalent alcohol highly compatible of urethane raw, therefore can be with them aptly as the UV light absorber of the urethane that stands pyroprocessing.If desired, can be with the UV light absorber of benzyl formamidine compound as makeup and plastics.
Described benzyl formamidine compound adds as UV light absorber in the manufacturing processed of plastics.At this moment, the benzyl formamidine compound adds with conventional amount used, and is preferably based on the plastic raw materials solids content of 100 weight parts, and the add-on of benzyl formamidine compound is 0.1～5.0 weight part.
Hereinafter, the present invention will more at large describe with reference to following examples.Following examples are used for helping to understand the present invention, it should be considered as limiting the scope of the invention.
＜embodiment 1 〉
N, the preparation of N '-two (4-carbethoxy phenyl)-N '-benzyl carbonamidine
Under 43 ± 3 ℃, under agitation 329.58g benzocaine (benzocaine) is dissolved in the 800ml toluene, then 118.78g85% formic acid is dropwise added wherein.Said mixture was reacted 2 hours down at 100 ± 5 ℃, thereby obtain solid product (a).
Under agitation gained solid product (a) is dissolved in the 500ml toluene, the 200ml aqueous solution with tertiary butyl bromination ammonium (8.12g) and NaOH (150.04g) dropwise adds wherein then, subsequently to wherein adding bromotoluene (170.04g).Under agitation make said mixture reaction 1.5 hours.With the gained organic layer from reaction mixture, separate, dry and reduction vaporization, thereby obtain solid product (b).
Under 30 ℃, when stirring, gained solid product and benzocaine are dissolved in the 500ml toluene, then with 340.44gPOCl
3Dropwise add wherein.Under 70 ℃ ± 3 ℃, under agitation make said mixture reaction 5 hours.Under 20 ℃, gained solution is dropwise joined in the 500ml 20%NaOH aqueous solution.The gained organic layer is separated from reaction mixture, washs, uses Na with the 300ml saturated brine solution
2SO
4Drying, filtration and reduction vaporization, thus thick product obtained.
In the solution of ethyl acetate (EA) and hexane (Hex) (1: 1), above-mentioned thick product is carried out recrystallization, thereby obtain 325.5g (productive rate: final solid phase prod 37.8%).
The structure of gained solid phase prod is passed through
1H NMR spectrum (CDCl
3, 200MHz) obtain confirming.
Its
1H NMR spectrum is shown among Fig. 1.Concrete data are as follows:
1H NMR(CDCl
3，200MHz)δ：1.36～1.43(m，6H)，4.29～4.40(m，4H)，7.06(d，2H，J＝6.8Hz)，7.19(d，2H，J＝8.7Hz)，7.31～7.34(m，5H)，7.98(d，2H，J＝2.2Hz)，8.00(d，2H，J＝2.0Hz)，8.37(s，1H)
The structure of gained solid phase prod is passed through
1H NMR spectrum (CDCl
3, 200MHz) obtain confirming.Its
1H NMR spectrum is shown among Fig. 1.Concrete data are as follows:
NMR (nucleus magnetic resonance) analysis revealed gained solid product is the N of formula 8, N '-two (4-carbethoxy phenyl)-N '-benzyl carbonamidine.
＜embodiment 2 〉
N-3, the preparation of 5-two-tertiary butyl-4-hydroxy benzyl-N '-4-carbethoxy phenyl-N-phenyl formamidine
With 40.00g 2,6-two-tertiary butyl-4-methylphenol and 36.1g N-bromine succinimide join in the 400ml chloroform, and then under agitation with 2.90g 2,2 '-Diisopropyl azodicarboxylate adds wherein.With this reaction mixture refluxed 19 hours.After above-mentioned reaction mixture cooling, filtering, the filtrate that obtains is washed with 400ml water.The gained organic layer is separated, uses Na from reaction mixture
2SO
4Dry, dry also reduction vaporization obtains 51.50g (productive rate: solid product (a) 94%).
Dividually, 14.6ml aniline is joined in the 80ml toluene, dropwise adding is wherein with 9.70ml formic acid then.Said mixture was reacted 2 hours down at 100 ℃ ± 5 ℃, and water is removed from reaction mixture.After this, make above-mentioned reaction mixture be cooled to room temperature, filtration and water and wash, thereby obtain solid product (b).
Under agitation gained solid product (b) is dissolved in the 80ml toluene, the 100ml aqueous solution with tertiary butyl bromination ammonium (4.90g) and NaOH (5.60g) dropwise adds wherein then, subsequently to wherein adding 20.0g solid product (a).Under agitation make said mixture reaction 2 hours.The gained organic layer is separated, uses Na from reaction mixture
2SO
4Drying is also carried out reduction vaporization, thereby obtains 12.1g (productive rate: solid product (c) 53%).
Under 40 ℃, when stirring, gained solid product (c) and 9.3g benzocaine are dissolved in the 200ml toluene, then with 7.20mlPOCl
3Dropwise add wherein.Under 70 ℃ ± 3 ℃, under agitation make said mixture reaction 6 hours.Under 20 ℃, gained solution is dropwise joined in the 270ml10%NaOH aqueous solution.The gained organic layer is separated from reaction mixture, washs, uses Na with the 80ml saturated brine solution
2SO
4Dry, filter and carry out reduction vaporization, thereby obtain thick product.
In the solution of EA and Hex (1: 7), above-mentioned thick product is carried out recrystallization, thereby obtain 10.8g (productive rate: final solid phase prod 43%).
The structure of gained solid phase prod is passed through
1H NMR spectrum (CDCl
3, 200MHz) obtain confirming.
Its
1H NMR spectrum is shown among Fig. 2.Concrete data are as follows:
1H NMR(CDCl
3，200MHz)δ：1.35～1.42(m，21H)，4.35(q，2H，J＝7.0Hz)，5.12(s，1H)，5.15(s，2H).7.05(d，2H，J＝8.3Hz)，7.12(s，2H)，7.15～7.34(m，5H)，7.99(d，2H，J＝8.7Hz)，8.15(s，1H)
NMR analysis revealed gained solid phase prod is the N-3 of formula 7,5-two-tertiary butyl-4-hydroxy benzyl-N '-4-carbethoxy phenyl-N-phenyl formamidine.
＜embodiment 3 〉
N, N '-two (4-carbethoxy phenyl)-N-3, the preparation of 5-two-tertiary butyl-4-hydroxy benzyl carbonamidine
Under 43 ± 3 ℃, under agitation the 10.0g benzocaine is dissolved in the 50ml toluene, then 7.2ml formic acid is dropwise added wherein.Said mixture was reacted 2 hours down at 100 ℃ ± 5 ℃, and water is removed from reaction mixture.After this, make above-mentioned reaction mixture be cooled to room temperature, filtration and water and wash, thereby obtain 10.2g (productive rate: solid product (a) 88%).
Under agitation gained solid product (a) is dissolved in the 20ml toluene, the 100ml aqueous solution with tertiary butyl bromination ammonium (1.1g) and NaOH (1.26g) dropwise adds wherein then, subsequently to wherein adding 3,5-two-tertiary butyl-hydroxybenzyl bromine (4.5g).Under agitation make said mixture reaction 2 hours.The gained organic layer is separated, uses Na from reaction mixture
2SO
4Drying is also carried out reduction vaporization, thereby obtains 3.35g (productive rate: solid product (b) 55%).
Under 40 ℃, when stirring, gained solid product (b) and 1.4g benzocaine are dissolved in the 100ml toluene, then with 1.1mlPOCl
3Dropwise add wherein.Under 70 ℃ ± 3 ℃, under agitation make said mixture reaction 6 hours.Under 20 ℃, gained solution is dropwise joined in the 75ml10%NaOH aqueous solution.The gained organic layer is separated from reaction mixture, washs, uses Na with the 50ml saturated brine solution
2SO
4Dry, filter and carry out reduction vaporization, thereby obtain thick product.
In the solution of EA and Hex (1: 6), above-mentioned thick product is carried out recrystallization, thereby obtain 2.0g (productive rate: final solid phase prod 45%).
The structure of gained solid phase prod is passed through
1H NMR spectrum (CDCl
3, 200MHz) obtain confirming.
Its
1H NMR spectrum is shown among Fig. 3.Concrete data are as follows:
1H NMR(CDCl
3，200MHz)δ：1.33～1.44(m，24H)，4.36(q，4H，J＝6.8Hz)，5.14(s，1H)，5.23(s，2H)，7.05(d，2H，J＝12.9Hz)，7.12(s，2H)，7.22(d，2H，J＝11.2Hz)，7.98(d，4H，J＝9.9Hz)，8.30(s，1H)
NMR analysis revealed gained solid phase prod is the N of formula 9, N '-two (4-carbethoxy phenyl)-N-3,5-two-tertiary butyl-4-hydroxy benzyl carbonamidine.
＜embodiment 4 〉
N-4-butoxy carbonyl phenyl-N '-4-carbethoxy phenyl-N-3, the preparation of 5-two-tertiary butyl-4-hydroxy benzyl carbonamidine
Under 43 ± 3 ℃, under agitation the 17.4g benzocaine is dissolved in the 20ml toluene, then 5.4ml formic acid is dropwise added wherein.Said mixture was reacted 2 hours down at 100 ℃ ± 5 ℃, and water is removed from reaction mixture.After this, make above-mentioned reaction mixture be cooled to room temperature, filtration and water and wash, thereby obtain 19.6g (productive rate: solid product (a) 98%).
Under agitation 12.6g solid phase prod (a) is dissolved in the 150ml toluene, the 80ml aqueous solution with tertiary butyl bromination ammonium (4.2g) and NaOH (4.8g) dropwise adds wherein then, subsequently to wherein adding 3,5-two-tertiary butyl-4-hydroxy bromotoluene (17.0g).Under agitation make said mixture reaction 2 hours.The gained organic layer is separated, uses Na from reaction mixture
2SO
4Drying is also carried out reduction vaporization, thereby obtains 13.2g (productive rate: solid product (b) 53%).
Under 40 ℃, when stirring, gained solid product (b) and 5.5g benzocaine are dissolved in the 100ml toluene, then with 4.2gmlPOCl
3Dropwise add wherein.Under 70 ℃ ± 3 ℃, under agitation make said mixture reaction 6 hours.Under 20 ℃, gained solution is dropwise joined in the 250ml10%NaOH aqueous solution.The gained organic layer is separated from reaction mixture, washs, uses Na with the 50ml saturated brine solution
2SO
4Dry, filter and carry out reduction vaporization, thereby obtain thick product.
In the solution of EA and Hex (1: 5), above-mentioned thick product is carried out recrystallization, thereby obtain 9.5g (productive rate: final solid phase prod 53%).
The structure of gained solid phase prod is passed through
1H NMR spectrum (CDCl
3, 200MHz) obtain confirming.
Its
1H NMR spectrum is shown among Fig. 4.Concrete data are as follows:
1H NMR(CDCl
3，200MHz)δ：0.97(t，3H，J＝7.2HZ)，1.36～1.53(m，23H)，1.64～1.82(m，2H)，4.28～4.42(m，4H)，5.14(s，1H)，5.23(s，2H).7.06(d，2H，J＝8.5Hz)，7.12(s，2H)，7.23(d，2H，J＝8.8Hz)，8.01(d，4H，J＝9.1Hz)，8.30(s，1H)
NMR analysis revealed gained solid phase prod is N-4-butoxy carbonyl phenyl-N '-4-carbethoxy phenyl-N-3 of formula 10,5-two-tertiary butyl-4-hydroxy benzyl carbonamidine.
＜experimental example 1 〉
To the compound N of the formula 8 that makes among the embodiment 1, N '-two (4-carbethoxy phenyl)-N '-benzyl carbonamidine and measure as the UV specific absorption and the thermostability of compound N-(4-carbethoxy phenyl)-N '-methyl-N '-phenyl formamidine of the formula 11 of conventional UV light absorber.
Use chloroform (100ml) solution of each sample of 1mg that the UV specific absorption is measured.Described mensuration uses UV spectrograph (Bechman Du-600) to carry out.Gained the results are shown among Fig. 5.Under nitrogen atmosphere, the temperature of each sample raises with 15 ℃/minute speed, and (Rerkin-Elmer TGA7) measures thermostability by thermogravimetric analysis.Gained the results are shown among table 1 and Fig. 6.
Formula 11
Table 1
| Temperature (℃) | N, N '-two (4-carbethoxy phenyl)-N '-benzyl carbonamidine | N-(4-carbethoxy phenyl)-N '-methyl-N '-phenyl formamidine |
| Weightless (%) | Weightless (%) | |
| 150 | 100.0 | 100.0 |
| 200 | 100.0 | 99.6 |
| 230 | 100.0 | 98.5 |
| 250 | 99.9 | 96.5 |
| 280 | 99.0 | 88.8 |
| 300 | 97.6 | 77.4 |
| 350 | 82.6 | 8.7 |
From Fig. 5, can obviously find out, compound N of the present invention, the absorption of UV of the absorption of UV of N '-two (4-carbethoxy phenyl)-N '-benzyl carbonamidine and compound N-(4-carbethoxy phenyl)-N '-methyl-N '-phenyl formamidine is suitable.
In contrast, from result shown in table 1 and Fig. 6 as can be seen, compound N of the present invention, the thermostability of N '-two (4-carbethoxy phenyl)-N '-benzyl carbonamidine is better than the thermostability of compound N-(4-carbethoxy phenyl)-N '-methyl-N '-phenyl formamidine.
＜experimental example 2 〉
In the production process of polyurethaneurea elastic fiber, with formula 8 compound Ns of preparation among the embodiment 1, N '-two (4-carbethoxy phenyl)-N '-benzyl carbonamidine and formula 11 compound Ns-(4-carbethoxy phenyl)-N '-methyl-N '-phenyl formamidine adds as UV light absorber respectively.
1800) and 1.7 mole 4 particularly, (molecular weight:, the 4-methyl diphenylene diisocyanate mixes, and makes it 90 ℃ of reactions 90 minutes down then, thereby prepares the prepolymer that two ends have isocyanate group with 1 mole of polytetramethylene glycol.The gained prepolymer is cooled to after 40 ℃, and with N, N '-N,N-DIMETHYLACETAMIDE adds wherein, thereby prepares about 45% pre-polymer solution.The gained pre-polymer solution is cooled to 5 ℃.Under vigorous stirring, based on the equivalents of prepolymer, in pre-polymer solution, slowly add the N of 96 equivalent % quadrols and 6 equivalent % diethylamine, N '-dimethylacetamide solution, thereby prolong and termination (terminate) prepolymer chain, form polyurethane urea solutions.Based on solids content (100 weight part), in above-mentioned polyurethane urea solutions, add formula 8 compound Ns that prepare among the embodiment 1 of respective amount shown in the following table 2 respectively, N '-two (4-carbethoxy phenyl)-N '-benzyl carbonamidine and formula 11 compound Ns-(4-carbethoxy phenyl)-N '-methyl-N '-phenyl formamidine is as UV light absorber.Said mixture is spun into (spun), thereby produces corresponding polyurethaneurea elastic fiber.
Use utilizes fading-o-measuring device meter (fade-o-meter) of xenon arc lamp, and polyurethaneurea elastic fiber (40 Denier (deniers)) is exposed 40 hours under ultraviolet ray.(Scinco Co., Ltd. Korea) measure the colour-change (Δ b value) of handling front and back with color controller.Gained the results are shown in the following table 2.
Table 2
| N, the amount (weight part) of N ' two (4-carbethoxy phenyl)-N '-benzyl carbonamidine | - | 0.5 | 1.0 | 1.5 | - | - | - |
| The amount (weight part) of N-(4-carbethoxy phenyl)-N '-methyl-N '-phenyl formamidine | - | - | - | - | 0.5 | 1.0 | 1.5 |
| Colour-change (Δ b) | 21.5 | 4.3 | 3.1 | 2.5 | 5.8 | 5.1 | 4.8 |
As can be seen from Table 2, excellent heat resistance based on benzyl formamidine compound of the present invention, with to compare, use the finished product of benzyl carbonamidine UV light absorber to show good performance with the conventional phenyl formamidine UV light absorber that benzyl carbonamidine UV light absorber same amount uses.
Industrial applicibility
As can be known clear and definite from foregoing description, because benzyl formamidine compound of the present invention has high UV absorbing properties and good thermostability, therefore can be used as the UV light absorber that stands pyroprocessing or need the plastics of excellent heat stability aptly.Particularly, the benzyl formamidine compound is used to make the plastics that stand pyroprocessing as UV light absorber, makes plastics have high UV absorbing properties, strengthened the wearing quality of plastics thus.
Although for illustrative purposes preferred implementation of the present invention is disclosed, but those skilled in the art are to be understood that, multiple modification, interpolation and replacement all are feasible, and this does not deviate from as the disclosed scope of the invention and spirit in the claims of enclosing.
Claims (22)
1, a kind of benzyl formamidine compound, this compound is represented by following formula 2:
Formula 2
Wherein, R
1And R
2Be selected from hydrogen, C independently of one another
1-9Alkyl and C
1-4Carbalkoxy, L
1And L
3Be selected from hydrogen and C independently of one another
1-4Alkyl, L
2Be selected from H and OH.
2, benzyl formamidine compound according to claim 1, wherein, R in the formula 2
1Be ethoxycarbonyl, the compound of described formula 2 is represented by following formula 3:
Formula 3
R wherein
2Be selected from hydrogen, C
1-9Alkyl and C
1-4Carbalkoxy, L
1And L
3Be selected from hydrogen and C independently of one another
1-4Alkyl, L
2Be selected from H and OH.
3, benzyl formamidine compound according to claim 2, wherein, R in the formula 3
2Be hydrogen, the compound of described formula 3 is represented by following formula 4:
Formula 4
L wherein
1And L
3Be selected from hydrogen and C independently of one another
1-4Alkyl, L
2Be selected from H and OH.
4, benzyl formamidine compound according to claim 3, wherein, L in the formula 4
1And L
3Be the tertiary butyl, L
2Be OH, the compound of described formula 4 is represented by following formula 7:
Formula 7
5, benzyl formamidine compound according to claim 2, wherein, R in the formula 3
2Be ethoxycarbonyl, described formula 3 compounds are represented by following formula 5:
Formula 5
L wherein
1And L
3Be selected from hydrogen and C independently of one another
1-4Alkyl, L
2Be selected from H and OH.
6, benzyl formamidine compound according to claim 5, wherein, L in the formula 5
1, L
2And L
3Be hydrogen, the compound of described formula 5 is represented by following formula 8:
Formula 8
7, benzyl formamidine compound according to claim 5, wherein, L in the formula 5
1And L
3Be the tertiary butyl, L
2Be OH, the compound of described formula 5 is represented by following formula 9:
Formula 9
8, benzyl formamidine compound according to claim 2, wherein, R in the formula 3
2Be butoxy carbonyl, the compound of described formula 3 is represented by following formula 6:
Formula 6
L wherein
1And L
3Be selected from hydrogen and C independently of one another
1-4Alkyl, L
2Be selected from H and OH.
9, benzyl formamidine compound according to claim 8, wherein, L in the formula 6
1And L
3Be the tertiary butyl, L
2Be OH, the compound of described formula 6 is represented by following formula 10:
Formula 10
10, a kind of UV light absorber, this UV light absorber is represented by following formula 2:
Formula 2
Wherein, R
1And R
2Be selected from hydrogen, C independently of one another
1-9Alkyl and C
1-4Carbalkoxy, L
1And L
3Be selected from hydrogen and C independently of one another
1-4Alkyl, L
2Be selected from H and OH.
11, UV light absorber according to claim 10, wherein, R in the formula 2
1Be ethoxycarbonyl, the compound of described formula 2 is represented by following formula 3:
Formula 3
R wherein
2Be selected from hydrogen, C
1-9Alkyl and C
1-4Carbalkoxy, L
1And L
3Be selected from hydrogen and C independently of one another
1-4Alkyl, L
2Be selected from H and OH.
12, UV light absorber according to claim 11, wherein, R in the formula 3
2Be hydrogen, L
1And L
3Be the tertiary butyl, L
2Be OH, the compound of described formula 3 is represented by following formula 7:
Formula 7
13, UV light absorber according to claim 11, wherein, R in the formula 3
2Be ethoxycarbonyl, L
1, L
2And L
3Be hydrogen, the compound of described formula 3 is represented by following formula 8:
Formula 8
14, UV light absorber according to claim 11, wherein, R in the formula 3
2Be ethoxycarbonyl, L
1And L
3Be the tertiary butyl, L
2Be OH, the compound of described formula 3 is represented by following formula 9:
Formula 9
15, UV light absorber according to claim 11, wherein, R in the formula 3
2Be butoxy carbonyl, L
1And L
3Be the tertiary butyl, L
2Be OH, the compound of described formula 3 is represented by following formula 10:
Formula 10
The benzyl formamidine compound that adds following formula 2 in the process of 16, a kind of plastics, these plastics plastic raw materials by being selected from synthetic resins, natural resin and polymerizable polymkeric substance at molding makes as UV light absorber:
Formula 2
R wherein
1And R
2Be selected from hydrogen, C independently of one another
1-9Alkyl and C
1-4Carbalkoxy, L
1And L
3Be selected from hydrogen and C independently of one another
1-4Alkyl, L
2Be selected from H and OH.
17, plastics according to claim 16, wherein, R in the formula 2
1Be ethoxycarbonyl, the compound of described formula 2 is represented by following formula 3:
Formula 3
R wherein
2Be selected from hydrogen, C
1-9Alkyl and C
1-4Alkoxy carbonyl, L
1And L
3Be selected from hydrogen and C independently of one another
1-4Alkyl, L
2Be selected from H and OH.
18, plastics according to claim 17, wherein, based on the plastic raw materials solids content of 100 weight parts, the add-on of described benzyl formamidine compound is the 0.1-5.0 weight part.
19, plastics according to claim 18, wherein, R in the formula 3
2Be hydrogen, L
1And L
3Be the tertiary butyl, L
2Be OH, the compound of described formula 3 is represented by following formula 7:
Formula 7
20, plastics according to claim 18, wherein, R in the formula 3
2Be ethoxycarbonyl, L
1, L
2And L
3Be hydrogen, the compound of described formula 3 is represented by following formula 8:
Formula 8
21, plastics according to claim 18, wherein, R in the formula 3
2Be ethoxycarbonyl, L
1And L
3Be the tertiary butyl, L
2Be OH, the compound of described formula 3 is represented by following formula 9:
Formula 9
22, plastics according to claim 18, wherein, R in the formula 3
2Be butoxy carbonyl, L
1And L
3Be the tertiary butyl, L
2Be OH, the compound of described formula 3 is represented by following formula 10:
Formula 10
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020040037886 | 2004-05-27 | ||
| KR1020040037886A KR100562428B1 (en) | 2004-05-27 | 2004-05-27 | Benzylformamidine compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1956947A true CN1956947A (en) | 2007-05-02 |
| CN100509765C CN100509765C (en) | 2009-07-08 |
Family
ID=35450806
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005800161572A Active CN100509765C (en) | 2004-05-27 | 2005-05-26 | Benzylformamidine compounds and plastic products containing the benzylformamidine compounds as ultraviolet light absorbers |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP4369978B2 (en) |
| KR (1) | KR100562428B1 (en) |
| CN (1) | CN100509765C (en) |
| WO (1) | WO2005115973A1 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101481331B (en) * | 2009-01-20 | 2013-02-13 | 常州市阳光药业有限公司 | N,N'-bis(4-ethoxy carbonyl phenyl)-N'-benzyl formamidine |
| TWI633079B (en) * | 2017-06-12 | 2018-08-21 | 和新化學工業股份有限公司 | Ultraviolet absorber and plastic article having the ultraviolet absorber |
| CN110804156A (en) * | 2019-11-07 | 2020-02-18 | 中天科盛（上海）企业发展股份有限公司 | High-strength anti-aging thermoplastic polyurethane elastomer and preparation method thereof |
| CN112047859A (en) * | 2018-04-26 | 2020-12-08 | 常州永和精细化学有限公司 | Method for preparing N, N '-di (4-ethoxycarbonylphenyl) -N' -benzylformamidine from waste residues generated in UV-1 production |
| CN113480451A (en) * | 2021-08-04 | 2021-10-08 | 天津利安隆新材料股份有限公司 | Amidine ultraviolet absorbent, preparation method and application thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4021471A (en) * | 1974-04-18 | 1977-05-03 | Givaudan Corporation | Formamidines useful as ultraviolet light absorbers |
| US4663876A (en) * | 1985-01-28 | 1987-05-12 | Reaume Robert N | Stock assembly kit and rifle embodying the same |
| US5011628A (en) * | 1988-06-15 | 1991-04-30 | Givaudan Corporation | N,N'-diarylbenzamidines useful as ultraviolet light absorbers |
| US5243055A (en) * | 1990-12-19 | 1993-09-07 | Givaudan Corporation | Heterocyclic formamidines useful as ultraviolet light absorbers |
| KR970001314A (en) * | 1995-06-19 | 1997-01-24 | Novel Formamidine Compounds | |
| JP3821544B2 (en) | 1997-07-02 | 2006-09-13 | ケミプロ化成株式会社 | Formamidine compound and ultraviolet absorber using the same |
-
2004
- 2004-05-27 KR KR1020040037886A patent/KR100562428B1/en active IP Right Grant
-
2005
- 2005-05-26 WO PCT/KR2005/001553 patent/WO2005115973A1/en active Application Filing
- 2005-05-26 CN CNB2005800161572A patent/CN100509765C/en active Active
- 2005-05-26 JP JP2007514898A patent/JP4369978B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101481331B (en) * | 2009-01-20 | 2013-02-13 | 常州市阳光药业有限公司 | N,N'-bis(4-ethoxy carbonyl phenyl)-N'-benzyl formamidine |
| TWI633079B (en) * | 2017-06-12 | 2018-08-21 | 和新化學工業股份有限公司 | Ultraviolet absorber and plastic article having the ultraviolet absorber |
| CN112047859A (en) * | 2018-04-26 | 2020-12-08 | 常州永和精细化学有限公司 | Method for preparing N, N '-di (4-ethoxycarbonylphenyl) -N' -benzylformamidine from waste residues generated in UV-1 production |
| CN112047859B (en) * | 2018-04-26 | 2023-11-03 | 常州永和精细化学有限公司 | Method for preparing N, N '-di (4-ethoxycarbonylphenyl) -N' -benzyl formamidine from waste residues generated in production of UV-1 |
| CN110804156A (en) * | 2019-11-07 | 2020-02-18 | 中天科盛（上海）企业发展股份有限公司 | High-strength anti-aging thermoplastic polyurethane elastomer and preparation method thereof |
| CN113480451A (en) * | 2021-08-04 | 2021-10-08 | 天津利安隆新材料股份有限公司 | Amidine ultraviolet absorbent, preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100509765C (en) | 2009-07-08 |
| WO2005115973A1 (en) | 2005-12-08 |
| JP4369978B2 (en) | 2009-11-25 |
| KR100562428B1 (en) | 2006-03-17 |
| JP2008500333A (en) | 2008-01-10 |
| KR20050112699A (en) | 2005-12-01 |
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