Photopolymerizable compositions

 

(57) Abstract:

Photopolymerizable compositions for the manufacture of photopolymer products by stereolithography without air-based oligoribonucleotide contains triethyleneglycoldinitrate (TGM-C), magyarkanizsa compound of formula 1, where n = 2, R = -(CH2-CH2-OH)3- unsaturated monomer is butylmethacrylate and photoinitiator - 2,2-dimethoxy-2-phenylacetophenone. Achieved increase in the rate of curing of the composition and reduce its volumetric shrinkage during curing, i.e., the reduction of manufacturing cycle parts and improving their accuracy characteristics. 2 Il., table 1.

The invention relates to photopolymerizable compositions based on unsaturated polyesters that can be used for the manufacture of parts by means of laser-induced polymerization (stereolithography) without access of air.

Known photopolymerizable compositions for the manufacture of photopolymer products, including oligoribonucleotides structuring agent, such as triethyleneglycoldinitrate (TGM-3), the unsaturated monomer is butylmethacrylate (BMA), photoinitiator, for example 2,2-dimethoxy-2-phenylacetate is wearing, wt.%:

Oligoribonucleotides - 70

Structuring agent, triethyleneglycoldinitrate - 10

Unsaturated monomer, butylmethacrylate - 18

Photoinitiator, 2,2-dimethoxy-2-phenylacetophenone - 2

However, the known arrangement has a low curing rate due to the high content of unsaturated monomer is butyl methacrylate and a large volumetric shrinkage affecting accuracy characteristics of the obtained details.

The objective of the invention is to increase the speed of curing of the composition and reduce its volumetric shrinkage during curing, i.e., the reduction of manufacturing cycle parts and improving their accuracy characteristics.

This is achieved by the fact that in addition, the structuring agent is proposed to use mediolanense compound of General formula (1)

< / BR>
with the copper content in Triethylenetetramine 0.2 wt.%.

The components of the composition are taken in the following ratio, wt.%:

Oligoribonucleotides - 80-86

Triethyleneglycoldinitrate - 1-6

Mediolanense compound of General formula (1) - 4-9

Butylmethacrylate - 1-8

2,2 dimethoxy-2-phenylacetophenone - 2-3

Comparative analysis with protOgO the introduction of a new component, namely liquid magyarkanizsa compounds of General formula (1). Thus, the proposed solution meets the criterion of "novelty".

Mediolanense compound of General formula (1) is new, not described in the literature. It was obtained by the reaction coordinate, using fine copper powder (fraction of 1-5 μm in the amount of 50% of the total composition of the powder) in an amount of 1 wt.% and triethyleneglycoldinitrate in the amount of 99 wt.%. After obtaining a steady dark blue staining liquid (dissolution was performed in the dark with occasional stirring), it was separated from the precipitate by decantation. In the study of fluid from spectrophotometry revealed that it contains 0.2 wt.% copper in terms of the total number of Triethylenetetramine. In Fig. 1 shows the photoelectron spectrum of O1s(in the energy range 530-536 eV) magyarkanizsa compounds of General formula (1). The first peak (ECBO1s= 531 eV) corresponds to 10% of oxygen atoms associated with the copper atoms. Since the copper content, calculated on the total number of Triethylenetetramine is 0.2% using x-ray photoelectronic spectroscopy established that the compound of General formula (1) in the IR spectrum (Fig. 2) magyarkanizsa compounds of General formula (1) in the field of 1800-1200 cm-1the separation of the double bond peak at 1636 cm-1and the appearance of the peak at 1600 cm-1witness the interaction formed of copper ions with the electrons of the double bond, which, obviously, leads to an increase in its reactivity.

Characteristics of the obtained magyarkanizsa the compounds of formula (1):

- density 20= 1,082 g/cm3;

- dynamic viscosity20= 0,012 Pas;

- the molar extinction coefficient (=325 nm) = 398,8 l/malism.

Example 1. Mixing 80 wt.% oligoribonucleotide, 1 wt.% Triethylenetetramine, 9 wt.% magyarkanizsa compounds of General formula (1), 8 wt.% the butyl methacrylate, 2 wt.% 2,2 dimethoxy - 2-phenylacetophenone. The composition is placed in the cell attachment ATR IR spectrometer Specord M-80" and is irradiated through the filter UFS-2 ( = 300-400 nm region wavelength of industrial UV lasers) ultraviolet lamp KD - L at a distance of 10 cm Through a certain time are shooting IR spectra of the composition. Calculating the speed of curing is carried out at the ratio of optical densities at 1636 cm-1(deformation vibrations of the double bond) and 1450 cm-1

Example 2 is Mixed 83 wt.% oligoribonucleotide, 3.5 wt.% Triethylenetetramine, 6.5 wt. % magyarkanizsa compounds of General formula (1), 4.5 wt.% of butyl methacrylate and 2.5 wt.% 2,2-dimethoxy-2-phenylacetophenone. The photopolymerization composition is carried out analogously to example 1.

Example 3 is Mixed 86 wt.% oligoribonucleotide, 6 wt.% Triethylenetetramine, 4 wt.% magyarkanizsa compounds of General formula (1), 1 wt. % of butyl methacrylate and 3 wt.% 2,2-dimethoxy-2-phenylacetophenone. The photopolymerization composition is carried out analogously to example 1.

The increase of the content in the composition magyarkanizsa compounds of General formula (1) above the maximum value leads to optical opacity of the composition and, consequently, to a significant reduction in the rate of laser photopolymerization. The decrease in composition magyarkanizsa compounds of General formula (1) below the minimum value leads to a reduction in the rate of photopolymerization.

Thus, the characteristics of the photopolymerizable compositions shown in the table, pokazyvaniya with prototype thereby reducing the manufacturing cycle of a product, and the relative volumetric shrinkage is reduced by 6-15%, therefore, improve the accuracy characteristics of the products obtained.

The sources of information.

1. Ephraim A. A. Development oligoadenylate compositions laser curing stereolithography. Abstract of thesis. Kida. Sciences / KSTU, Kazan, 1996, 18 S. (prototype).

Photopolymerizable compositions for the manufacture of photopolymer products by stereolithography without air-based oligoribonucleotide structuring agent - Triethylenetetramine (TGM-3), unsaturated monomer is butyl methacrylate and photoinitiator-2,2-dimethoxy-2-phenylacetophenone, characterized in that it further as a structuring agent contains mediolanense compound of General formula I

< / BR>
where n = 2,

R = -(CH2- CH2- O)3--,

with the copper content in Triethylenetetramine 0.2 wt.% in the following ratio, wt.%:

Oligoribonucleotides - 80 - 86

Triethyleneglycoldinitrate - 1 - 6

Mediolanense compound of General formula I - 4 - 9

Butylmethacrylate - 1 - 8

2,2-dimethoxy-2

 

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