CN100537611C - Free radical polymerization method having reduced premature termination, and product formed thereby - Google Patents
Free radical polymerization method having reduced premature termination, and product formed thereby Download PDFInfo
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- CN100537611C CN100537611C CNB2006101536045A CN200610153604A CN100537611C CN 100537611 C CN100537611 C CN 100537611C CN B2006101536045 A CNB2006101536045 A CN B2006101536045A CN 200610153604 A CN200610153604 A CN 200610153604A CN 100537611 C CN100537611 C CN 100537611C
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Abstract
A method of polymerizing by a free radical polymerization mechanism, product formed thereby, and apparatus for performing this method, are disclosed. The composition to be polymerized by the free radical polymerization mechanism is irradiated by a substantially constant radiation, the radiation being substantially without pulsation. The use of the substantially constant radiation without pulsation reduces premature termination of the polymerization. The substantially constant radiation can be the output of a lamp powered by a constant current, direct current power supply.
Description
The application is that international application no is PCT/US02/16652, international filing date is that national applications number was 02816540.3 after the PCT international application on May 29th, 2002 entered China's stage, denomination of invention is divided an application for the Chinese patent application of " reducing too early terminated free radical polymerisation process, the product that carries out the equipment of this method and form thus ".
Technical field
The present invention relates to a kind of polymerization process, wherein said polyreaction produces by radical polymerization mechanism; And relate to equipment that is used for this method and the polymerisate that makes by this method, particularly reduced the early stopping of crossing of polyreaction.The present invention is applicable to the polyreaction of material, wherein, described polymerization mechanism is radical polymerization, to wanting the polymeric material without limits, for example, it is suitable for having the polyreaction of the material of the two keys of C=C, and at this, described polyreaction causes by for example using up (as UV-light) irradiation according to mechanism of free-radical polymerization.
Background technology
In the light-initiated radical polymerization process of routine, use for example microwave-driven, electrodeless ultraviolet lamp, utilize the rectification alternating-current or the pulse power to produce microwave.These microwaves produce the pulsed ultraviolet light from electrodeless ultraviolet lamp, as being used for light-initiated light.Be that the described rectification alternating-current or the pulse power produce the pulse light output from lamp, be used for light-initiated described polyreaction.But this ordinary method forms the low product of bad molecular weight, and its productive rate is also low.
Therefore, require to make the high polymeric reaction product of molecular weight with high yield, and the molecular weight distribution of the product (polymkeric substance) that forms is narrower, forms with higher relatively speed simultaneously according to mechanism of free-radical polymerization.Promptly require to improve to cause formed product, improve the molecular weight (molecular weight increase) of its productive rate (productive rate height) and the product that forms, and reduce the distribution (scope) of the product that forms by irradiation (for example, light such as UV-light) according to mechanism of free-radical polymerization.
Summary of the invention
The inventor has been found that described Raolical polymerizable crosses early stopping and can cause productive rate low, and the molecular weight of the product that forms is low, and its reason provides the light-initiated pulsed light output of Raolical polymerizable.Be found to be the basis with this, the present invention provides constant irradiation (for example, light) all the time in polymerization process, and for example constant light intensity is come initiated polymerization (providing light-initiated) thus, and kept described polyreaction.
In addition in the present invention, by using constant output (temporarily), direct supply to obtain the output of constant light.For example (be not limited thereto), can use the direct supply of constant output (for example, constant current) to produce microwave, be used to drive the lamp that energy is provided by microwave, all the time produce the output of constant (evenly), successive light thus, be used for light-initiated, thereby reduced early stopping.In the present invention, for example can use the direct supply of described constant (evenly) electric current, constant current is provided all the time, make magnetron produce the microwave (for example) that drives described lamp, microwave produces the output of constant light by lamp (electrodeless lamp), carries out polyreaction thus.By constant light output (constant intensity, not fluctuation) is provided, reduced too early termination, and reduced at least owing to cross the disadvantageous effect that early stopping causes.
In another example, (for example, constant current) direct supply provides energy for Jupiter, produces constant (evenly), the output of successive light (constant intensity, not fluctuation) thus all the time can to use constant output, be used for light-initiatedly, reduce too early termination thus.
Therefore, can form improved polymerisate, described product property improves, and its molecular weight is higher, and molecular weight distribution (scope) reduces, and can prepare described polymerisate with higher speed (for example, when forming sheet material, can form described cured product) with higher linear velocity.
Description of drawings
Fig. 1 (a) illustrates in the routine techniques, uses the ultraviolet lamp of microwave-driven that the energy of initiated polymerization is provided, and uses rectification alternating-current or pulse dc power to produce microwave, the system of solidifying (polymerization) polymkeric substance; Fig. 1 (b) has shown the electric current output of the power supply that is used to produce the required microwave of microwave-driven ultraviolet lamp and the funtcional relationship of time; Fig. 1 (c) has shown the UV-light output of described lamp and the funtcional relationship of time.
Fig. 2 (a) illustrates in the illustrated embodiment of the present invention, uses the ultraviolet lamp of microwave-driven that the energy of initiated polymerization is provided, and uses direct supply to produce microwave, the system of solidifying (polymerization) polymkeric substance; Fig. 2 (b) has shown the funtcional relationship of the electric current output time of the power supply that is used to produce the required microwave of microwave-driven ultraviolet lamp; Fig. 2 (c) has shown the UV-light output of described lamp and the funtcional relationship of time.
Fig. 3 is the schematic circuit of direct supply, in illustrated embodiment of the present invention, can be used for producing the required microwave of lamp of microwave-driven, and described lamp produces the output of constant light, initiated polymerization thus.
Embodiment
Though will it should be understood that the present invention in conjunction with specifically and preferred embodiment illustrating, this limits the present invention in those embodiments anything but.On the contrary, this is to be used to cover all substitute modes, change and equivalents, and they are included in the described spirit and scope of the invention of appending claims.
In whole specification sheets, when thinking that material, method and apparatus comprise or comprise concrete component or structure or concrete processing step, the inventor thinks that material of the present invention, method and apparatus also be made up of described component or structure or described processing step basically.
In declaratives of the present invention, the present invention carries out described method and improves formed product by free radical polymerisation process, equipment.In illustrative method of the present invention, composition was carried out in the time of polyreaction, ray (not having pulse basically) with substantially constant shines described composition, cause thus and keep described Raolical polymerizable, described composition comprises by Raolical polymerizable and carries out polymeric material (for example, monomer or oligopolymer).This technology produces improved product, and it has high-performance, and can make described product with higher speed (higher turnout).And, the equipment that is used to produce the ray of substantially constant (for example comprises ray that produces substantially constant and the irradiation source that does not have pulse basically, but be not limited to light source, as UV-light), and direct supply for example, it exports constant current, the ray that is used to produce substantially constant and does not have pulse basically.Illustrate, described irradiation source can be the ultraviolet lamp of microwave-driven, and it has the direct supply that constant current is applied to microwave generator and produces the microwave that is used to drive described ultraviolet lamp.By using substantially constant and not having the ray of pulse, can reduce the early stopping of crossing of Raolical polymerizable at least.
The situation of the high molecular free radical that stops increasing by the little elementary free radical from the light trigger photolysis has been described in too early termination in the process that forms polymkeric substance by radical polymerization mechanism.This produces under pulsed irradiation, and at this moment, it is also short that described pulse-repetition ratio reaches the required time of " stable state " (stable state is meant that free radical formation speed equals the state of terminated speed (speed of coupling between free radical and the free radical)).The high molecular free radical (growth attitude) that increases, its termination speed is lower, and its reason is that the viscosity and the high molecular free radical size of polymerisation medium increases the very large transport property restriction that is caused soon.After light first pulse, most elementary free radical will promote to increase, and be accompanied by Raolical polymerizable, join (for example, acrylic double bond is an acrylate this polymeric monomeric substance) in the described pair of key.Under short pulse situation more, residual not photolytic light trigger begin to produce new elementary freedom in minor affairs base, compare the high molecular free radical of growth, its transport property is much higher.Therefore substantially, these elementary freedom in minor affairs bases that just produced by light trigger photodissociation subsequently (causing) by pulsed ultraviolet light will promote by and the diradical termination of the high molecular free radical coupling that increases, compete mutually with the new chainpropagation of initiation thus, thereby cause polyreaction to cross early stopping.
Among the present invention,, and use constant not have the light output of pulse, reduce the photolysis of the light trigger of preferential termination polyreaction all the time by avoiding pulsed light.In addition, (for example, produce the microwave that is used to drive described lamp, at this, this lamp is the electrodeless lamp of microwave-driven for the lamp that illumination is provided provides energy by using constant current DC power supply; Perhaps provide energy for Jupiter), can obtain constant intensity (for example, constant UV-light output) effectively, reduce above-mentioned too early termination, and reduce bad influence at least.
Though the Raolical polymerizable that the present invention is used in combination by the light trigger of UV-activated describes, the present invention is not limited to this.Promptly, be used to as required (for example activate described Raolical polymerizable, but be not limited to activate the initiator that is used to cause Raolical polymerizable) energy (for example, luminous energy), the present invention includes the light (for example, visible light, infrared light etc.) that uses constant light output (not having pulse or fluctuation basically), uses other type, the radiation of using other type.
Fig. 1 (a) has shown the routine techniques that is used for the composition Raolical polymerizable, and described composition forms the surface 7 (for example, the coating on the base material) of workpiece.This routine techniques uses rectification alternating-current or pulse dc power 1 to provide to produce the required microwave of microwave-driven ultraviolet lamp 3, produces UV-light 11 and activates light trigger in the composition that forms workpiece surface 7.Fig. 2 (a) has described among the present invention, uses DC power supply 5 to drive microwave-driven ultraviolet lamp 13, produces UV-light 15, activates the light trigger in the composition that forms workpiece surface 7, causes Raolical polymerizable thus.Fig. 1 (b) and 2 (b) have shown power supply 1 and 5 electric currents that produce and the funtcional relationship of time separately, have shown what routine techniques and the present invention produced separately in Fig. 1 (c) and 2 (c), are applied to light output 11,15 and the function of time on the workpiece surface 7.Arrow shown in the label 9 has indicated the travel direction of workpiece surface 7 through lamp 3,13.
Shown in Fig. 1 (b), in routine techniques, power supply 1 produces pulsed current, and from Fig. 1 (c) as seen, the UV-light 11 that is produced by lamp 3 is pulses.As mentioned above, the light of this pulse can cause Raolical polymerizable to cross early stopping.
From Fig. 2 (b) and 2 (c) as seen, provide constant current by power supply 5 among the present invention, and produce constant light output 15 all the time, be applied on the workpiece surface by ultraviolet lamp 13; As mentioned above, this has reduced crosses early stopping, has reduced adverse influence at least, and its productive rate raising, and molecular weight of product is higher.
In Fig. 3, shown the DC power supply that can be used for each side of the present invention.This DC power supply is to can be used for a kind of illustrative power supply of the present invention, is not intended to limit the invention.The high-voltage output that this power supply will have constant current all the time for example is applied on the magnetron, and at this, described lamp is the electrodeless lamp of microwave-driven.Described magnetron produces the microwave that is used to drive described lamp, and this lamp produces the output of constant light all the time.Described DC power supply also can be used for providing energy for Jupiter.
More specifically, Fig. 3 has shown a kind of three-phase AC line voltage, carries out rectification by three phase bridge 20 after flow through linear filter and contact.Described three phase bridge 20 can be applied to dc voltage on the H electric bridge 30.Pre-charge-relay (and dependent resistor) 25 and electrical condenser 27 can be set between described three phase bridge 20 and H electric bridge 30.Described pre-charge-relay (and dependent resistor) 25 can prevent by the caused infringement of rush current for electrical condenser 27 chargings.Electric bridge 30 can comprise four insulating grid bipolar transistors (IGBT) of being arranged to the H shape.Be in operation, the diagonal angle transistor of described H electric bridge 30 conducts electricity in a half-open pass circulation simultaneously, and then, other diagonal angle transistor of H electric bridge 30 is conduction in a remaining half-open pass circulation.This operation can be applied to alternating-current in high-tension transformer and rectification (HVTR) assembly 40.Described transistor can reduce the size and the weight of described high-tension transformer thus in high frequency (20kHz according to appointment) operation down.When using higher running frequency, also can reduce and be used to make the smooth filter part of electric current that is applied on the magnetron.
Phase shifter/pulse-width modulator 50 can be used to control igbt transistor.The input of phase shifter/pulse-width modulator 50 can be magnetron current and voltage, and they are measured on HVTR assembly 40.Phase shifter/pulse-width modulator 50 can be regulated transistorized control signal, the curtage when making it regulate 40 outputs of HVTR assembly.This method can be called feedback control.
HVTR assembly 40 can comprise the transformer of many outputs.Each output can be carried out rectification with independent rectifier and wave filter electrical equipment.Described filter circuit can comprise energy-storage travelling wave tube (as inductor block and electrical condenser), eliminates described high-frequency impulse, and the electric current that is essentially DC is provided for magnetron.Described each rectifier output can be connected and be produced the required high-voltage of magnetron.
If need, engine pilot circuit 60 can monitor and control whole power supply.Described engine pilot circuit comprises the time variable control microprocessor, and it has necessary input/output circuitry, is used to monitor builtin voltage and electric current.
The invention is not restricted to any particular type monomer () polyreaction for example, esters of acrylic acid, and can be used for the polyreaction (that is free radical system) of being undertaken by mechanism of free-radical polymerization.For example, no matter other structure in the molecule, more or less easy of the two keys of the C=C of the free redical polymerization of any type crosses early stopping, and the present invention uses and is applied to the constant light of wanting on the polymeric composition and exports and reduce this too early termination.
The various materials that the present invention is suitable for below will be discussed.But what should emphasize is, below only is the embodiment of the commercially available reaction system of terminated too early easily for example, and this is because they carry out Raolical polymerizable, and the present invention is not limited to these reaction systems.
The first kind material that the present invention is suitable for is that those pass through Raolical polymerizable, i.e. the homopolymerization of chainpropagation type forms the material of homopolymer.In this case, only use two keys of one type, but described pair of key can being connected on any main chain by chemistry, and, the two keys of the C=C of any amount can be connected on any main chain.Typical example is esters of acrylic acid and methyl acrylic ester.In the present invention, vinylbenzene and styrene derivatives, N-vinylamide and vinyl acetate also are the exemplary of C=C structure, and they can carry out polymerization by Raolical polymerizable, and have benefited from providing all the time the use of the Constant Direct Current power supply of constant light output.
The second class material that the present invention is suitable for is those materials by chainpropagation type copolyreaction formation multipolymer.It can use different monomer or oligopolymer described in homopolymerization.Can use the different monomers of any amount or the mixture of oligopolymer with the two keys of the C=C of any ratio and above-mentioned any type, this depends on the reactive behavior ratio of each monomer/oligomer, and formed multipolymer has very different character.Typical example is acrylate/methacrylate, acrylate/unsaturated polyester and acrylate/N-vinylamide.
The 3rd class material that the present invention is suitable for is the material that forms multipolymer by the alternating copolymerization reaction.In this case, any receptor type (A) monomer of any amount and arbitrary proportion or its mixture can mix (near the mol ratio of 1:1) with give arbitrarily build (D) monomer or its mixture of any amount and arbitrary proportion, carry out the alternating copolymerization reaction.For this situation, more than and not mentioned additional quantity comprise substituent potential and commercially available monomer of having of C=C key and oligopolymer.These comprise A and D type monomer, and they can not carry out above-mentioned homopolymerization.In U.S. Patent No. 5,446, among 073 (Jonsson etc.), various receptor types have been described and have given the build monomer that its content is all with reference to being incorporated in this.Typical embodiment is fumaric acid esters/Vinyl Ether, maleic acid ester/Vinyl Ether and maleimide/Vinyl Ether.
As mentioned above, the many dissimilar polyreaction of carrying out according to Raolical polymerizable all will be benefited from the present invention.The above type is not the material that only can use, and can use the material of other type, as long as polyreaction is carried out according to Raolical polymerizable.
The present invention is applicable to any polymerization technique of carrying out according to Raolical polymerizable.Can polymerization single polymerization monomer and oligopolymer in the polyreaction of the present invention.Can comprise the molecule that comprises a C=C at least by the polymeric monomer among the present invention, it can carry out polymerization by Raolical polymerizable.This monomer can comprise the C=C key of various types of any amount with arbitrary proportion, and it can carry out Raolical polymerizable.
Below will list the embodiment of each side of the present invention, and compare, show that the effect that the present invention obtains is better.These embodiment of the present invention use constant current (all the time), direct supply, and provide and shine the constant light output of wanting on the polymeric composition, and and use the embodiment of variable power supply to compare the irradiates light that described variable power supply provides existence to fluctuate (pulsed light).Described composition is shone, and carries out Raolical polymerizable thus, and forming thickness is the film of 15-25 micron, and this controls by Teflon partition or coiling scraper.Described filming in the presence of the air and do not have all can solidify under the conditions of air.Listed in the following table 1 with described speed (fpm: respectively the filming feet per minute clock) through irradiation light.Described composition comprises the Irgacure 184 as light trigger, and it is the 1-hydroxycyclohexylphenylketone.Described composition comprises the Irgacure 184 of the following stated amount, and comprises as monomeric isobornyl acrylate, HDDA (hexanediyl ester) or vinylformic acid ethoxylated nonylphenol ester, and they carry out polymerization by Raolical polymerizable.In the Raolical polymerizable of photoinitiator system, also can use CHVE (cyclohexanedimethanol divinyl ether) and EMI (N-ethyl maleimide) as monomer.
Among the present invention, following embodiment uses " OMNI " DC power supply (seeing the power supply diagram of Fig. 3) to come to provide constant current as the ultraviolet lamp of microwave-driven, and it is all the time with the described composition of constant UV-light output irradiation.For comparison techniques, described " VPS-3 " power supply provides pulsed current, when described electric current is applied to the ultraviolet lamp of microwave-driven, produces the output of pulse (fluctuation) UV-light.
From following result as seen, two keys (C=C) transformation efficiency of cure formulations of the present invention is higher by 7% than what use comparison techniques to obtain approximately.As following result as seen, to have the translational speed of the substrate passed irradiates light of filming thereon especially remarkable when higher for the advantageous results that obtains of the present invention.
Table 1
A. homopolymerization--comprise the isobornyl acrylate of 0.25% Irgacure 184
25fpm 50fpm 100fpm 150fpm 200fpm
VPS-3 91％ 89％ 84％ 69％ 51％
91％ 90％ 82％ 67％ 44％
92％ 90％ 84％ 69％ 44％
52％
Average 91% 90% 83% 68% 48%
OMNI 92％ 91％ 85％ 73％ 55％
92％ 91％ 85％ 72％ 55％
91％ 91％ 85％ 73％ 53％
44％
Average 92% 91% 85% 73% 52%
Table 2
B. homopolymerization--comprise the isobornyl acrylate of 2% Irgacure 184
25fpm 50fpm 100fpm 150fpm
VPS-3 96％ 95％ 91％ 87％
96％ 95％ 92％ 88％
96％ 96％ 92％ 86％
Average 96% 95% 92% 87%
OMNI 96％ 95％ 92％ 90％
96％ 95％ 92％ 90％
97％ 95％ 91％ 90％
Average 96% 95% 92% 90%
Table 3
C. homopolymerization--comprise the hexanediyl ester (HDDA) of 0.125%Irgacure 184
25fpm 50fpm 100fpm 150fpm
VPS-3 85％ 80％ 65％ 42％
87％ 81％ 62％ 45％
86％ 83％ 60％ 39％
41％
Average 86% 81% 62% 42%
OMNI 86％ 84％ 66％ 46％
86％ 83％ 68％ 49％
84％ 66％ 46％
53％
Average 86% 84% 67% 49%
Table 4
D. homopolymerization--comprise the vinylformic acid ethoxylated nonylphenol ester of 0.3% Irgacure 184
Use OMNI to carry out the difference that two keys transform with different curing speeds with VPS-3
75fpm 100fpm 125fpm 150fpm
VPS-3 78.1％ 62.5％ 57.4％ 53.3％
77.6％ 66.7％ 53.9％ 50.5％
80％ 67.1％ 58.6％ 47.6％
78.6％ 68.2％ 58.5％ 45.9％
76％ 63.9％ 52.9％ 49.9％
Average 78.1% 65.7% 56.3% 49.4%
OMNI 74.8％ 63.8％ 59％ 50.3％
77.9％ 72.2％ 63.6％ 50.1％
81.2％ 71.7％ 62.2％ 50.9％
85.9％ 69％ 62.5％ 52.6％
78.4％ 66.4％ 57.3％ 52.7％
Average 79.6% 68.6% 60.9% 51.3%
Table 5
E. copolymerization--comprise isobornyl acrylate/1 of 0.2% Irgacure 184,6-HDDA (1: 1 mol ratio)
Use OMNI to carry out the difference that two keys transform with different curing speeds with VPS-3
50fpm 75fpm 100fpm 125fpm 150fpm
VPS-3 89.6％ 83.9％ 80.4％ 70.2％ 54％
89.9％ 84.9％ 73.6％ 71.1％ 50.9％
88.9％ 84.3％ 79.1％ 67.4％ 50.4％
87.3％ 86.3％ 77.7％ 58％ 46.9％
91.4％ 86.8％ 79.7％ 61.2％ 41.1％
Average 89.4% 85.2% 78.1% 65.6% 48.7%
OMNI 90.9％ 83.8％ 82.8％ 71％ 59％
90.4％ 86.9％ 83.3％ 77.3％ 54.6％
90.9％ 87.8％ 82.1％ 72.6％ 50.6％
85.7％ 80.9％ 76.5％ 49.2％
89.5％ 82.1％ 64％ 47.9％
Average 90.7% 86.7% 82.2% 72.3% 52.3%
Table 6
F. alternating copolymerization-cyclohexanedimethanol divinyl ether/N-ethyl maleimide (1:2 mol ratio)
Use OMNI to carry out the difference that two keys transform with different curing speeds with VPS-3
75fpm 100fpm 125fpm
VPS-3 86.3％ 76.4％ 73.5％
(maleimide) 88.8% 79.9% 74.2%
70.7％ 74.4％ 69.2％
80.5％ 88.6％ 77.1％
79.8％ 63％
Average 81.2% 76.5% 73.5%
VPS-3 61.0％ 57％ n/a
(vinyl ether) 59.2% 57%
51.6％ 56％
56.3％ 67.7％
55.5％ 44.2％
Average 56.7% 56.4%
OMNI 91％ 79.2％ 74.7％
(maleimide) 94.6% 82.9% 82.5%
78.2％ 73.8％ 82.8％
89.9％ 94％ 76.2％
82.7％ 81.8％
Average 87.3% 82.3% 79.1%
OMNI 64.5％ 61.8％ 57.5％
(vinyl ether) 68.8% 65.4% 59.4%
60％ 53.6％ 59.8％
65.1％ 63.1％ 58.9％
62.2％ 60.4％
Average 64.1% 60.9% 58.9%
In table 7 and 8, shown the comparison of gel permeation chromatography (GPC) measurement that the comparative sample of the present invention's use " OMNI " power supply solidified sample and use " VPS-3 " power supply has been done.Gained molecular weight (Mw) distribute the narrowly distributing clearly illustrate that use " OMNI " power supply solidified sample many.This is because when using " OMNI " power supply, short polymer chain part much less.
Table 7
G. the GPC result of isobornyl acrylate/Irgacure 184 (0.25%), it solidifies in inert nitrogen with different curing speeds
The residence time (min) Mw Mw * d (peak width)
VPS-3/HP6(10fpm) 15.392 94177 106889 3.1280
OMNI/HP6(10fpm) 15.450 90079 103974 3.0639
VPS-3/HP6(200fpm) n/a n/a 230923 4.8724
OMNI/HP6(200fpm) n/a n/a 197038 4.7655
Mw is the molecular-weight average under the retention time.
Mw* is that whole molecular-weight average distributes.
Table 8
H. the GPC result of isobornyl acrylate/Irgacure 184 (2%), it with different curing speeds in air set
The residence time (min) Mw Mw * d (peak width)
VPS-3/HP6(10fpm) 15.945 62405 68089 2.2914
OMNI/HP6(10fpm) 15.990 60357 68408 2.1793
VPS-3/HP6(20fpm) 16.186 52193 56010 2.2848
OMNI/HP6(20fpm) 16.239 50182 55842 2.2150
VPS-3/HP6(200fpm) 17.240 23889 50471 2.4988
OMNI/HP6(200fpm) 17.237 23942 43293 2.2061
Mw is the molecular-weight average under the retention time.
Mw* is that whole molecular-weight average distributes.
Therefore, (for example, constant output light as UV-light, but is not limited thereto to use the irradiation of constant output among the present invention; Can use other exposure light such as infrared light and visible light), can reduce the early stopping of crossing of polyreaction.And, can improve the conversion of monomer, especially when described composition passes through irradiates light at a high speed to polymkeric substance; Can improve the molecular weight of (increase) resulting polymers, and reduce the distribution (scope) of molecular weight in the polymerisate, and physics and other character of improving resulting polymers.
Claims (4)
1. the product that forms by free radical polymerisation process, described method comprises:
A kind of composition is provided, and described composition comprises the material that can carry out Raolical polymerizable;
Use the described composition of radiation exposure that produces by lamp, cause thus and keep described Raolical polymerizable, make the described material polymerization in the described composition, wherein, in described polymerization process, described composition all the time with constant, do not have the radiation exposure of pulse.
2. the described product of claim 1, it is characterized in that, with the described composition of UV-irradiation, cause thus and keep described Raolical polymerizable, described UV-light is produced by electrodeless lamp, the microwave-driven that described electrodeless lamp is produced by microwave generator, and described microwave generator provides energy by constant current, direct supply, and also described composition also comprises light trigger.
3. the described product of claim 1 is characterized in that, with UV-irradiation described composition, causes thus and keeps described Raolical polymerizable, and described UV-light is produced by Jupiter, and described Jupiter provides energy by constant current, direct supply.
4. the described product of claim 1 is characterized in that, the described material that carries out Raolical polymerizable comprises at least a material in esters of acrylic acid and the methyl acrylic ester.
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| US09/938,208 | 2001-10-23 |
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| CN104854140A (en) * | 2012-12-14 | 2015-08-19 | 3M创新有限公司 | Method of polymerizing ethylenically-unsaturated materials using ionizing radiation |
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| US4181752A (en) * | 1974-09-03 | 1980-01-01 | Minnesota Mining And Manufacturing Company | Acrylic-type pressure sensitive adhesives by means of ultraviolet radiation curing |
| US4886840A (en) * | 1986-02-27 | 1989-12-12 | Kohjin Co., Ltd. | Diluent for UV and EB curable resins |
| US5506279A (en) * | 1993-10-13 | 1996-04-09 | Minnesota Mining And Manufacturing Company | Acrylamido functional disubstituted acetyl aryl ketone photoinitiators |
-
2002
- 2002-05-29 CN CNB2006101536045A patent/CN100537611C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4181752A (en) * | 1974-09-03 | 1980-01-01 | Minnesota Mining And Manufacturing Company | Acrylic-type pressure sensitive adhesives by means of ultraviolet radiation curing |
| US4053814A (en) * | 1976-07-14 | 1977-10-11 | Gte Laboratories Incorporated | Continuous automatic starting assist uv circuit for microwave powered electrodeless lamps |
| US4886840A (en) * | 1986-02-27 | 1989-12-12 | Kohjin Co., Ltd. | Diluent for UV and EB curable resins |
| US5506279A (en) * | 1993-10-13 | 1996-04-09 | Minnesota Mining And Manufacturing Company | Acrylamido functional disubstituted acetyl aryl ketone photoinitiators |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104854140A (en) * | 2012-12-14 | 2015-08-19 | 3M创新有限公司 | Method of polymerizing ethylenically-unsaturated materials using ionizing radiation |
| CN104854140B (en) * | 2012-12-14 | 2017-09-01 | 3M创新有限公司 | Utilize the method for the unsaturated material of ionising radiation ethylenical |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1931884A (en) | 2007-03-21 |
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