CN102442909A - Low-volatility and low-mobility benzoyl formate - Google Patents

Abstract

The invention provides compounds shown in structural formula I. In the formula, n represents 2-10. These compounds have extremely low volatility and mobility, and can be independently used as photoinitiators or be mixed with other photoinitiators for the photopolymerization process of unsaturated carbon-carbon double-bond compounds.

Description

Low volatilization low migration benzoyl-manthanoate

Technical field

The application relates to low volatilization low migration benzoyl-manthanoate, is mixed for preparing the photopolymerization composite that contains unsaturated carbon-carbon double bond compounds as light trigger or with other light trigger separately.

Background technology

For example the benzoyl-manthanoate is used in various compsns as light trigger independently among US4038164, US4475999, EP132868A1 and the GB1534320A1 at patent documentation, played the effect of photopolymerization.But; In the actual use of photopolymerizable coatings, it should be noted that the pollution problem that the small molecular weight light trigger exists after, to light trigger demand constantly increase of low volatility and low migration along with the expansion of coating consumption; For example require the coating of the low migration of low smell to use very extensive at civil areas such as paper, floors; Especially there is strict more examination criteria to define material migration amount for the food and medicine wrapping material, many small molecular weight material are got rid of outside the inventory that allows, like UVNUL MS-40; 2-hydroxyl-2 methyl-phenyl-1-acetone; The molecular weight of compounds such as benzoyl-methyl-formiate, ethyl ester is little, in compsn construction with polymerization after, they all might be to contactant migration or volatilization and polluting in air.So patent US4507187 has disclosed the benzoyl-manthanoate that has siloxanes, US3930868 and US4308394 have disclosed the substituted benzene formyl carbamate that has acrylate group and have been connected on the resin through double-bond polymerization, thereby have lowered volatility.So obvious more complicated of preparation process has increased the cost of material, and has reduced the versatility of material.WO9833761 has disclosed the dibenzoyl manthanoate of terepthaloyl moietie, two polyoxyethylene glycol, three polyoxyethylene glycol as non-volatile light trigger, and in fact, the molecular weight of ethylene glycol bisthioglycolate benzoyl formiate has only 326; The molecular weight of Diethylene Glycol dibenzoyl manthanoate is 370, and is also not really desirable on the volatility of being heated, and still can perceive significantly smell; The actual measurement thermogravimetic analysis (TGA) shows; 10%, 250 ℃ of existing 20% weight loss of 200 ℃ of losses, loss 50% in the time of 300 ℃; Because hot volatility is big, smell and the performance of mobility aspect are not good enough; Poly glycol ether dibenzoyl manthanoate causes in the structure ether chain water-soluble bigger because unit alkylidene group chain length is too short, emulsification and water-soluble loss easily in manufacturing processed, and manufacturing cost is high; In use, such structured light initiator is prone to the moisture absorption, causes that composition system is unstable, after the film forming, also is to be soaked by water easily to dissolve migration, causes mobility high, so be not the light trigger of a good practicality.And when the unit alkylidene group long-chain in the poly glycol dibenzoyl manthanoate structure is long, can reduce the hardness of cured film; When poly glycol polymerization degree height, when molecular weight was excessive, effectively the content of functional group's benzoyl-methanoyl reduced, thereby reduces its efficiency of initiation, must strengthen addition and could guarantee solidification rate, cause use cost too high, so practicality is not strong yet simultaneously.

Summary of the invention

The application's purpose provides the compound of one type of low volatility low migration shown in structural formula I

N=2-10 wherein;

Preferred construction formula I compound, wherein n=2-6.Compare with benzoyl-methyl-formiate and poly glycol ether dibenzoyl manthanoate; They have had low-down volatility and low migration, and this compounds can be separately be mixed for the photopolymerization process of unsaturated carbon-carbon double bond compounds as light trigger or with other light trigger.

The preparation of the application's formula I compound is at first synthetic benzoyl-methyl-formiate and dimerization or poly 1; Transesterification reaction takes place in 4-butyleneglycol or their mixture under catalyst action, catalyzer is transesterification reaction for example sodium methylate, sodium ethylate, Dibutyltin oxide or a tosic acid commonly used.The washing normally well known to those skilled in the art of the treating processes of reaction solution, distillation etc.

One or several of formula I compound mixes as light trigger can carry out compound formation compsn radical polymerization, that contain unsaturated carbon-carbon double bond with at least a, and photopolymerization can take place.One of compound that contains unsaturated carbon-carbon double bond is meant the propenoate of monohydroxy-alcohol or polyvalent alcohol and other structure polyvalent alcohols, for example hexanediyl ester, polyester polyol propenoate; Next comprises vinyl ether, vinyl benzene etc.; Also have the ester, acid amides of unsaturated dicarboxylic acid etc. in addition.

Except that formula I compound, in compsn, can also contain one or more mixtures and the additive that improves composition properties of the known light trigger of other types; Known light trigger has UVNUL MS-40,2-isopropyl thioxanthone, 2-hydroxy-2-methyl-phenyl-1-acetone, 1-hydroxy-cyclohexyl phenyl ketone, 2-methyl-2-(4-morpholinyl)-(4-methylthio group) phenyl-1-acetone 2; 4,6-trimethylbenzoyl diphenyl phosphine oxide etc.; Additive comprises material as stablizer for example to methoxyl group phenol, 2-(2 '-hydroxyl-5 '-tert-butyl-phenyl) benzotriazole; As the material of polymerization promotor for example trolamine, p-(dimethylamino)-benzoic acid ester.In compsn, add additive such as matting agent, skimmer, flow agent etc., each item performance that can regulate compsn.

The consumption of formula I compound accounts for the 0.1-10% of composition weight, and consumption generally is that 1-6% can bring into play good photopolymerization.

Prepared compsn can be designed to be suitable for use on various substrate surfaces, for example paper, timber, plastics, metal, and, accomplish solidification process with normally used method coating of those skilled in the art and irradiation light.Benzoyl-formic acid ester compound method of manufacture provided by the invention is simple; When using as light trigger; Paint film after Photocurable composition before solidifying and the curing all has only low-down smell, low volatility and significantly reduced mobility; Meet on the photocuring industrial market and make being easy to, efficiency of initiation is higher, has the demand of low smell, low volatilization, low migrate attribute light trigger simultaneously.

Description of drawings

Fig. 1 is that proton nmr spectra data and structure are pointed out.

Fig. 2 is the TGA analytical results.

Embodiment

Following indefiniteness example will further specify teachings herein, but the content of the application's claim is not limited to cited embodiment.

Control Example 1

Method according to patent documentation WO9833761; Preparation Diethylene Glycol dibenzoyl manthanoate; Be about to 164g benzoyl-methyl-formiate, 106g Diethylene Glycol and the mixing of 10g Dibutyltin oxide and be stirred and heated to 120 ℃, and distill out methyl alcohol, unnecessary benzoyl-methyl-formiate is removed in last underpressure distillation; Obtain yellow-green liquid; High pressure liquid chromatographic analysis wherein contains benzoyl-methyl-formiate 2%, contains Diethylene Glycol list benzoyl-manthanoate 20%, contains diethylene glycol bis-benzoyl-manthanoate 78%.

Control Example 2

With waiting mole tetraethylene-glycol to replace Diethylene Glycol; Process and method by control Example 1 obtain yellow-green liquid; High pressure liquid chromatographic analysis wherein contains benzoyl-methyl-formiate 2%; Contain tetraethylene-glycol list benzoyl-manthanoate 23%, contain the two benzoyl-manthanoate 75% of tetraethylene-glycol.

Embodiment 1

The one two benzoyl formiates of dibutylene glycol that contract

In 500 milliliters of four-hole bottles, add 40.6 gram (0.25 moles) contract dibutylene glycol, 82.5 gram (0.5 mole) benzoyl-methyl-formiate and sodium methylate 4g, be warmed up to 130 ℃ of stirring reactions 5 hours, reclaim methyl alcohol simultaneously.Water washing is used in the cooling back, removes moisture under reduced pressure, gets 104.5 gram light yellow liquid products.High pressure liquid chromatographic analysis residue benzoyl-methyl-formiate content 0.50%, the one two benzoyl formic acid ester contents of dibutylene glycol that contract are 98.5%, and yield is 98%.Ultimate analysis measured value (theoretical value), C:67.28% (67.59%), H:6.11% (6.14%).The proton nmr spectra data are seen table 1; Structure is pointed out and is seen Fig. 1.

The table 1 one two benzoyl formiate proton nmr spectra data of dibutylene glycol that contract

Numbering	Chemical shift ppm	The peak type	Relative integral
				a	8.0114 with 7.9858	Bimodal	2
b	7.6774、7.6532、7.6284	Triplet	1
				c	7.532、7.5066、7.4814	Triplet	2
d	4.4416、4.4200、4.3981	Triplet	2
				e	5.4759、3.4554、3.4352	Triplet	2
f	1.9162、1.8947、1.8724、1.8459、1.8237	Quintet	2

[0024]

g

1.7384,1.7190,1.6919,1.6710,1.6521

Quintet

2

Embodiment 2

In 500 milliliters of four-hole bottles; Add 125.0 gram (0.5 mole) polytetramethylene glycols 250 and (contain the dibutylene glycol 33%, two that contracts three butyleneglycols 38%, three, four butyleneglycols 22% that contract that contract; Four five butyleneglycols 6% that contract; Five six butyleneglycols 1% that contract), 165.0 gram (1.0 moles) benzoyl-methyl-formiate and sodium methylate 8g, be warmed up to 130 ℃ of stirring reactions 8 hours, reclaim methyl alcohol simultaneously.Water washing is used in the cooling back, removes moisture under reduced pressure, gets 251.3 gram light yellow product.High pressure liquid chromatographic analysis residue benzoyl-methyl-formiate content 1.10%, all dibasic acid esters content add up to 98.15%, and yield is 97.4%, and product liquid chromatograph mass spectrography analytical results is seen table 2.

Table 2 liquid chromatograph mass spectrography analytical results

Embodiment 3

Thermogravimetic analysis (TGA)

Show that with the U.S. Q5000 of AT instrument company hot weightless instrument site-test analysis data benzoyl-methyl-formiate (MBF) is in 50%, 140 ℃ of i.e. volatilization fully of 120 ℃ of losses; 10%, 250 ℃ of existing 22% weight loss of 200 ℃ of losses of the sample of control Example 1, loss 50% in the time of 300 ℃; And the sample of embodiment 1 only loses 2%, 250 ℃ for 200 ℃ and only loses 5% weight, loss 20% in the time of 300 ℃, and the sample of illustrative embodiment 1 has remarkable improved heat resistance, and volatility is extremely low.Data plot is seen Fig. 2.

Embodiment 4

Curing performance relatively

To process corresponding ultraviolet curing clear coat composition as light trigger by the foregoing description 1,2 and control Example 1,2 prepared products and benzoyl-methyl-formiate.The prescription of said composition sees Table 3.

Table 3

The varnish of preparation executed printing on the tinplate with the excellent spreader of 10 micro wires, using a power is that the medium pressure mercury Jupiter is cured with 100 meters/component velocity in 100 watts/centimetre.Record obtains surface of good and thoroughly solidifies number of pass times under the needed lamp.Smell is 5 grades to the maximum, and minimum is 1 grade.The result is as shown in table 4.

The evaluation result of the different light triggers of table 4

Light trigger	The required number of pass times of completely solidified	The grading of film smell
			The benzoyl-methyl-formiate	2	5
Control Example 1	4	3
			Control Example 2	4	3
Embodiment 1	3	2
			Embodiment 2	4	1

The result shows that the film stink after the application's compound solidifies significantly is lower than the benzoyl-methyl-formiate, also is lower than the compound of control Example 1,2.

Embodiment 5

To process corresponding ultraviolet curing clear coat composition as light trigger by the foregoing description 2 and control Example 2 prepared products.The formula rate of said compsn is with table 3.

The varnish of preparation executed printing on 12 * 12cm white board with 15 micro wires rods spreader, using a power is that the medium pressure mercury Jupiter carries out 4 curing with 100 meters/component velocity in 100 watts/centimetre.To there be the part of cured film to be cut into 10 * 10cm, but be placed on leaching extract in 3% aqueous acetic acid, list in table 5 through analytical calculation mobility data.

The mobility evaluation result of the different light triggers of table 5

Light trigger	Mobility (μ g/kg)
		Control Example 2	20547
Embodiment 2	4652

The result shows that in the film after the curing, the mobility of the light trigger of embodiment 2 significantly is lower than the light trigger of control Example 2.

Claims (5)

1. compound in structural formula I,

N=2～10 wherein.

2. a compound as claimed in claim 1, wherein n=2～6.

3. photopolymerization composite, composition has:

(a) at least a can carry out compound radical polymerization, that contain unsaturated carbon-carbon double bond and

(b) at least a compound in structural formula I according to claim 1 as light trigger.

4. according to the photopolymerization composite of claim 3, wherein also contain other known light trigger as component (c) and other additives as component (d),

Wherein component (c) is one of benzophenone, Alpha-hydroxy ketone, alpha-amino group ketone or acylphosphine oxide class or its miscellany.

5. according to claim 3 or 4 described a kind of photopolymerization composites, wherein the weight content 0.1-10% of component (b).

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