CN1021055C - Asphalt emulsion - Google Patents

Asphalt emulsion Download PDF

Info

Publication number
CN1021055C
CN1021055C CN 85105866 CN85105866A CN1021055C CN 1021055 C CN1021055 C CN 1021055C CN 85105866 CN85105866 CN 85105866 CN 85105866 A CN85105866 A CN 85105866A CN 1021055 C CN1021055 C CN 1021055C
Authority
CN
China
Prior art keywords
starch
latex
emulsion
bitumen emulsion
dry weight
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 - Fee Related
Application number
CN 85105866
Other languages
Chinese (zh)
Other versions
CN85105866A (en
Inventor
R·B·穆尔
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from US06/638,790 external-priority patent/US4548966A/en
Application filed by BASF SE filed Critical BASF SE
Priority to CN 85105866 priority Critical patent/CN1021055C/en
Publication of CN85105866A publication Critical patent/CN85105866A/en
Application granted granted Critical
Publication of CN1021055C publication Critical patent/CN1021055C/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Landscapes

  • Compositions Of Macromolecular Compounds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

The viscosity of asphalt emulsion is controlled by the method that modified starch whose weight percentage content is as high as 1 % is added, and the modified starch is composed of no more than 27 % of amylose and amylopectin.

Description

Asphalt emulsion
The present invention relates to the modification of bituminous modification, particularly bitumen emulsion, so that it meets the standard of American Society Testing and Materials (ASTM) to the regulation of Sai Bote (Saybolt) viscosity of various rank bitumen emulsions.Pitch one speech that this standard specifications adopted had both comprised the pitch in naturally occurring pitch such as Te Linida (Trinidad) lake, comprised the synthetic asphalts of producing in the petroleum refinery again.
Before Holy Bible period, pitch by people as material of construction, said exceedingly high tower in the Holy Bible, when it is built in the mortar employed Gomorrah foundry loam be exactly pitch.Recently, the joint cement during pitch has been used to build the road.Bitumen emulsion also is widely used in building and the maintenance road surface.A current problem that runs into is too strong and energy and a Segregation of bitumen emulsion flowability heat or warm.If when especially bitumen emulsion was with the modification of a kind of synthetic polymer emulsion institute, this situation was even more serious.At least since the nineteen thirty, people have known and adopt synthetic polymer to come pitch is carried out modification.Have some textbooks that bituminous has been discussed and use and modification, comprising " pitch and their allied substances " arranged, the 5th edition, Haber Te Abaila Durham (Herbert Abraham) is write, and Van Nostrand press publishes; " pitch science and technology ", Yi Te Wien J crust thatch (Edwin, J, Barth) is write, and Gordon and Brcach press publishes; " pitch and road-making material, modern technologies ", John E Bai Erxun (John E.Parson) writes, and Noyes data company publishes, 1977; And " (MS-19), publish in March, 1979 for basic asphalt emulsion handbook, No. the 19th, pitch association handbook book series.
In the patent that the applicant can find, have only a kind of patent that the use of various natural thickeners in bitumen emulsion has been discussed.
Be presented to No. the 437674th, the English Patent of E.I.Du Pont Company November 4 nineteen thirty-five, announced the dispersion agent that a kind of pitch aqueous emulsions is used.This dispersion agent is a kind of alkali (comprising ammonium) of the alkylsurfuric acid that contains at least 8 carbon atom alkyls group or the salt of alkaline earth element.Also openly stated simultaneously " included thickening material has for example casein, egg white, binding agent, gelatin, resin or various starch, tannin, natural gum, dextrin and tapioca (flour), flour in the emulsion ...." the pH value of positively charged ion rapid hardening emulsion is about about 3.The pH value of conventional anionic emulsion is about about 12.Usually, unmodified starch at pH less than 5 or can be in just degrade than the short period greater than 10 o'clock.
Current, the back doping can not joined in the existing bitumen emulsion subsequently easily, to set up and to keep its viscosity.Usually, if a kind of viscosity of bitumen emulsion is too low, be necessary with this emulsion and a kind of emulsion fusion, to increase the viscosity of this bitumen emulsion with viscosity higher.
The invention provides a kind of can be with the pH value up to 10 the viscosity adjustment of bitumen emulsion under 122 to the method that can reach for 75 plug baud seconds at least, this method is included in the above-mentioned emulsion and adds weight percentage up to 1% treated starch, and these treated starches partly are made up of by amylopectin the amylose starch and the residue thereof that are no more than 27%.
The present invention also provides a kind of composition, and this pH value can comprise a kind of latex and a kind of treated starch up to 10 composition, and described latex is selected from following polymers:
A) a kind of C that contains 4-C 6The homopolymer of conjugated diolefine;
B) following monomeric a kind of multipolymer:
I) about 40% to 20%(weight) C 8-C 12Vinyl or vinylidene aromatic monomer, the monomer here can be non-substituted monomer, or by C 1-C 4The monomer that straight or branched alkyl, chlorine or bromine atom replace;
Ii) about 60-80%(weight) C 4-C 6Conjugated diolefine;
Iii) 0 to about 10%(weight) C 3-C 9Vinyl unsaturated carboxylic acid or its C 1-C 4Alkyl ester or alkyl alcohol ester, or its amide derivatives, this acid amides can be non-replacement or nearly 2 C are arranged on the N atom 1-C 4Alkyl or silane alcohol base is substituent and
C) following monomeric multipolymer:
I) up to about 40%(weight) C 3-6The alkene nitrile and
Ii) its remainder is a kind of C 4-6Conjugated diolefine,
The amount of described treated starch is a benchmark with the latex dry weight, and up to about 15%, this treated starch is formed by not being higher than 20% the amylose starch and the amylopectin of equal amount.
The present invention further provides a kind of pH value less than 10 contain the moisture modified pitch emulsion of 50% to 75% solid by weight, its dry weight constitutes:
A) about 84 pitches to about 99.9 parts (weight),
B) can be up to one of the following polymkeric substance of about 15 parts (weight):
I) a kind of C 4-6The homopolymer of conjugated diolefine,
The ii) multipolymer that constitutes by following monomer:
1) about 40% to 20%(weight) C 8-12Vinyl or vinylidene aromatic monomer, these monomers can be non-substituted monomers, or by C 1-4The monomer that straight chained alkyl or branched-chain alkyl, chlorine or bromine atom replace,
2) about 60 to 80%(weight) C 4-6Conjugated diolefine;
3) 0 to about 10%(weight) C 3-9Vinyl unsaturated carboxylic acid, or its C 1-4Alkyl ester or silane alcohol base ester, or its amide derivatives, this acid amides can be non-replacements, or 2 C are arranged on the N atom 1-4Alkyl or silane alcohol base substituent and
The iii) multipolymer that constitutes by following monomer:
1) up to 40%(weight) C 3-6The alkene nitrile;
2) its residue is a kind of C partly 4-6Conjugated diolefine; With
C) can be up to 1%(weight) treated starch, this starch partly is made up of by amylopectin the amylose starch and the residue that are not higher than 20%.
As used in this specification sheets, term " Sai Bote viscosity " is represented according to the D88 of American Society for Tests and Materials, the Sai Bote furol viscosity that records under 122 temperature.Rapid hardening cationic asphalt emulsion (CRS-2) viscosity number be should be 100 to 400 plug bauds second (ASTM-D2397-79).Highway structure be should be 75 to 400 plug bauds second (ASTM-D977) with rapid hardening negatively charged ion bitumen emulsion (RS-2) viscosity number.Bitumen emulsion will meet the standard specifications of RS-2 and CRS-2 bitumen emulsion.
Emulsion of the present invention is in 120 to 180 scopes of temperature, and from 2 to 24 hours time scope can keep its viscosity significantly not descend.
According to starch commonly used provided by the invention is waxy starches.In " starch chemistry and technology " I, II volume waxy starches is discussed to some extent, this book is edited by R.L.Whistler and E.F.Paschall, Science Press, and nineteen sixty-five publishes in New York.Waxy starches contains and is not more than 27% amylose starch, and its residue is an amylopectin partly.Preferably adopt amylose content less than 5% waxy starches, if amylose starch is just more desirable less than 1% o'clock.
Starch used in the present invention is modification.Preferably a kind of cross-linking starch.This cross-linking starch is to make by certain intermolecular reaction that starch and a kind of energy and two or more hydroxyl react.Suitable linking agent comprises formaldehyde, phosphoryl chloride, 3-chloro-1; 2-propylene oxide, three metaphosphoric esters, acetaldehyde, oxalic dialdehyde, vinyl sulphone, diepoxides class, 1; 3; 5;-trichlorine and 1; 3,5-triacryl-S-triazine, cyclohexane vulcabond, two (methylol) ethylidene-urea and N, N ' methylene bisacrylamide.This modification or cross-linking starch have supply of commodities.Less than 5 or greater than 7 o'clock, all unmodified starch are hydrolyzed to glucose at pH.Through the starch of modification at pH up to about 10 o'clock, still keep stable and be not degraded to glucose.A kind of useful especially product, its trade name is " Resista ", is to be sold by A.E.Staley manufacturing company.The present invention is not the preparation method who does not yet prepare to expand to this starch.
The pH value of bitumen emulsion of the present invention can be up to about 10.Preferable pH value is about 1.5 to 10, and the most desirable pH value scope is about 4 to 8.
It is benchmark with the bituminous dry weight that bitumen emulsion of the present invention is used up to 1%() waxy starches carries out modification.Preferable waxy starches content is that benchmark is about 0.05 to 0.5% with the pitch dry weight, and more desirable starch content is about 0.1% to 0.4%.Be that about 0.25% of benchmark is the best particularly with the pitch dry weight.
The more desirable starch method that adds is the starch that contains 50%, all the other be can miscible emulsifying agent as a kind of slurries, join in the bitumen emulsion.So-called mixable being meant is being mixable aspect the change of emulsifying agent and the adjusting of pH value.The slurries of most convenient are the bitumen emulsions that is made by about 20% starch and 80% moisture emulsifier system.Yet water can be used to form farinaceous size in many cases.Can take to make it to have minimum degree agglomerative step in some cases, for example control the method for adding speed, dry starch be joined in the bitumen emulsion go.This method is not suitable for the rapid hardening emulsion.Before the technical scale batching, bitumen emulsion and farinaceous size are carried out the laboratory batching earlier to observe the problem that whether exists such as forming coagulum.
Bitumen emulsion can further comprise a kind of synthetic polymer latex.In general, should contain 35% in this latex to 75%(weight) polymer beads, its pH value is less than about 10.Preferably a kind of rubber polymer of polymkeric substance in the latex.It can be a kind of C 4-6The homopolymer of conjugated diolefine; Or the multipolymer that generates by following monomer:
I) weight percentage is about 40 to 20 C 8-C 12Vinyl or vinylidene aromatic monomer, these monomers can be non-substituted monomers, perhaps by C 1-C 4The monomer that straight chained alkyl or branched-chain alkyl, chlorine or bromine atom replace;
Ii) contain weight percentage and be about 60 to 80 C 4-C 6Conjugated diolefine; With
Iii) weight percentage 0 is to up to about 10 C 3-C 9Vinyl unsaturated carboxylic acid, or its C 1-C 4Alkyl ester or silane alcohol base ester, or its amide derivatives, this acid amides can be non-replacements, or the C up to 2 is arranged on the N atom 1-4Alkyl or silane alcohol base are substituent;
Perhaps be the multipolymer that following monomer generates:
I) weight percentage is up to about 40 C 3-6The alkene nitrile; With
Ii) all the other partly are a kind of C 4-6Conjugated diolefine.
C 4-6Conjugated diolefine is divinyl and isoprene preferably.
Suitable C 8-12Vinyl or vinylidene aromatic monomer comprise vinylbenzene, alpha-methyl styrene, p-methylstyrene, chloro-styrene and bromstyrol.Preferable vinyl or vinylidene aromatic monomer are vinylbenzene, alpha-methyl styrene and p-methylstyrene.
Suitable carboxylic acid monomer comprises the vinyl unsaturated carboxylic acid, for example vinylformic acid, methacrylic acid, fumaric acid and methylene-succinic acid and their lower alkyl esters or silane alcohol base ester class and primary amide class, these acid amides can be non-replacements, perhaps on their N atom site C are arranged 1-4Alkyl or silane alcohol base are substituent.This class monomer comprises methyl acrylate, ethyl propenoate, Hydroxyethyl acrylate, methyl methacrylate, Jia Jibingxisuanyizhi, hydroxyethyl methylacrylate, acrylamide, Methacrylamide and N hydroxymethyl acrylamide.
Vinyl cyanide is a kind of preferably in the alkene nitrile.More desirable latex is latex natural rubber, styrene-butadiene copolymer and acrylonitrile butadiene copolymer.In styrene-butadiene copolymer, desirable styrene content is about 20 to 35 weight percent, and all the other partly are divinyl.Usually include at least 60% in the styrene-butadiene latex, best 65% solid.The preferred content of vinyl cyanide in acrylonitrile-butadiene copolymers is 28 to 34 weight percent, and solids content is about 35 to 50 weight percent in latex.
Can be with polymer latex, calculate by dried latex (being polymkeric substance) weight, with can be up to 15% of pitch dry weight, about 10% the amount of preferably not being higher than be added in the bitumen emulsion.This latex should have can with the aqueous emulsion medium pitch electrically charged compatible electric charge.Therefore, anionic latex should mix with the negatively charged ion bitumen emulsion, and cationic latex should mix with the cationic asphalt emulsion.The usage quantity of latex preferably can provide about 2% to 5%, best about 3% polymkeric substance to emulsion.Styrene-butadiene latex can make with cold polymerization, and can be negatively charged ion or cationic.And acrylonitrile-butadiene latex anionic preferably.As mentioned above, will tend to degraded at pH greater than about 10 o'clock according to modification waxy starches used in the present invention.Usually, can use natural soap, for example the soap class of Yatall MA, sylvic acid, lipid acid or long-chain vegetables oil is stablized anionic latex.These soap classes are very sensitive to the pH value, when the pH value less than 9 or 10 the time, effect will reduce.Therefore must adopt a kind of synthetic soap to stablize anionic latex, this synthetic soap was effective at pH less than 10 o'clock.To cause the raising of bitumen emulsion and latex price like this.
Before pitch and latex are carried out macro-mixing, mixes with pitch with latex in a small amount earlier, with definite pitch instability whether.
If pitch is to use latex modified, so, the fusion of giving of latex and starch is very easily.Starch is joined in the latex, calculate with the latex dry weight, add-on can reach 15% dry weight.Preferably adopt about dry weight more than 1%.For cationic latex, add preferably about 5% to the 15%(weight of amount of starch) (with the dry weight is benchmark, adds dry weight percentage ratio).For anionic latex, the amount that adds starch is about 1 to 15%(weight) (with the dry weight is benchmark, adds dry weight percentage ratio).
Following embodiment plans to illustrate optimum condition of the present invention.
Example 1
In cationic styrene one butadiene latex about 25% to 100 parts of styrene contents that calculate by dry weight, that cold polymerization makes, add the starch of the various content that are slurry condition.Then the pH value of latex is adjusted to the level of regulation.This latex/starch mixture being added in the cationic asphalt emulsion, is benchmark with the bituminous dry weight again, and add-on is 3% latex/starch dry weight.Modifying asphalt is kept certain hour under 158 °F.Write down the Sai Bote viscosity number of bitumen emulsion then.Experimental result is as shown in table 1.
Table 1
The latex of starch is 158 122 viscosity
Umber pH value hours Sai Bote second
The Ergon*CRS-2(contrast) 0 105
-latex does not exist
Latex 0 4.5 34
Avelex ＊ 1030 5 6.0 2 39
Avelex 1030 5 6.0 17 46
Avelex 1030 10 6.0 2 73
Avelex 1030 10 6.0 16 48
Avelex 1030 10 5.0 2 81
Avelex 1030 10 5.0 16 53
Avelex 1030 10 3.1 2 69
Avelex 1030 10 3.1 16 49
Avelex 1030 1.9 2 63
Avelex 1030 10 1.9 16 47
Sta-lock ＊ 10 5.0 2 211
Sta-lock 10 5.0 24 43
Ethylex ＊ 10 5.0 2 91
Ethylex 10 5.0 24 47
Resista ＊ 10 5.0 2 81
Resista 10 5.0 24 113
Ergon is a kind of trade name of cationic asphalt emulsion.
Following is the starch test product:
The yam starch of Avelex 1030-modification (trade(brand)name of U.S. Key Products Co., Ltd);
The yam starch of Sta-lock-modification (trade(brand)name of A.E.Staley manufacturing company);
The W-Gum of Ethylex-modification (trade(brand)name of A.E.Staley manufacturing company);
The waxy corn starch of Resista-modification (trade(brand)name of A.E.Staley manufacturing company).
From above-mentioned data as can be seen:
(1) do not have the latex of starch, the viscosity of bitumen emulsion is reduced;
(2) common, treated starch makes emulsion begin just to form certain viscosity, just descends but this kind viscosity of bitumen emulsion surpasses 2 hours 158 following shelf times of temperature;
(3) when improving the viscosity of bitumen emulsion with latex and modification waxy corn starch, the viscosity of emulsion continues to increase at 158 °F.
Example 2
To calculate about 10 parts modification waxy corn starch by dry weight, join that to be calculated as 100 parts of above-mentioned examples by the latex dry weight employed with in a kind of latex.The mixture that produces is joined in a kind of cationic asphalt emulsion, under 122 temperature, measure initial with four hours after the Sai Bote viscosity number.The cation emulsion of modification to be remained under 180 temperature when experimentizing.Its experimental result is expressed as follows:
Bitumen emulsion CRS-2 viscosity number=244 plug baud second
Bitumen emulsion is initial=195 plug baud seconds
+ 3% latex/CRS-2 viscosity number
180 of starch mixtures are after following 4 hours=182 plug baud seconds
Bitumen emulsion is initial=146 plug baud seconds
+ 5% latex/CRS-2 viscosity number
180 of starch mixtures are after following 4 hours=182 plug baud seconds
Bitumen emulsion is initial=46 plug baud seconds
+ 10% latex/CRS-2 viscosity number
180 of starch mixtures are after following 4 hours=153 plug baud seconds

Claims (1)

1, a kind of pH can consist of up to the moisture bitumen emulsion of 10 modification:
A) a kind of moisture bitumen emulsion;
B) a kind of by (i) and the (ii) latex of the multipolymer that produces of copolymerization, by the dry weight basis of moisture bitumen emulsion, its content is≤15% (dry weight):
(i) 40 to 20% C 8-12Vinyl or vinylidene aromatic monomer, these monomers can be non-substituted monomers, or by C 1-4Straight chained alkyl or branched-chain alkyl, the monomer that the chlorine or bromine atom replaces,
(ii) 60 to 80% C 4-6Conjugated diolefine; And
C) a kind of cross-linking starch, with the dry weight basis of described moisture bitumen emulsion, its content is≤1% (dry weight), this cross-linking starch comprises≤27% amylose starch, all the other are essentially amylopectin.
CN 85105866 1984-08-08 1985-08-02 Asphalt emulsion Expired - Fee Related CN1021055C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN 85105866 CN1021055C (en) 1984-08-08 1985-08-02 Asphalt emulsion

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US06/638,790 US4548966A (en) 1984-08-08 1984-08-08 Asphalt emulsion
CN 85105866 CN1021055C (en) 1984-08-08 1985-08-02 Asphalt emulsion

Publications (2)

Publication Number Publication Date
CN85105866A CN85105866A (en) 1987-02-04
CN1021055C true CN1021055C (en) 1993-06-02

Family

ID=25741924

Family Applications (1)

Application Number Title Priority Date Filing Date
CN 85105866 Expired - Fee Related CN1021055C (en) 1984-08-08 1985-08-02 Asphalt emulsion

Country Status (1)

Country Link
CN (1) CN1021055C (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106967362B (en) * 2017-03-23 2019-07-26 深圳市朗迈新材料科技有限公司 A kind of low temperature resistant asphalt waterproofing paint and preparation method thereof

Also Published As

Publication number Publication date
CN85105866A (en) 1987-02-04

Similar Documents

Publication Publication Date Title
JP5701763B2 (en) Road pavement using asphalt binder and asphalt emulsion
US6346561B1 (en) Pavement material
CN87103585A (en) cationic asphalt emulsion
CN1058605A (en) polymer blend
CN102417736A (en) Waste rubber powder modified asphalt and preparation method thereof
CN1140589C (en) Elastomer-modified bituminous compositions
CN1202179A (en) Fine polytetrafluoroethylene powder and production and uses thereof
US5704971A (en) Homogeneous crumb rubber modified asphalt
CN112266622B (en) Wheel-sticking-free emulsified asphalt and preparation method thereof
CN113088115B (en) A kind of modified asphalt for sleeper fire prevention and preparation method thereof
US5045576A (en) Latex conversion to cationic form use, for example in cationic asphalt emulsion
CN112679898A (en) Vinyl chloride-acrylate copolymer modified water-based asphalt and preparation method thereof
CN103849153A (en) High-viscosity high-elasticity pitch and preparation method thereof
CN109593371A (en) Road asphalt modifier and modified pavement asphalt and preparation method thereof and asphalt
CN1021055C (en) Asphalt emulsion
CN106832976B (en) Modified pitch and preparation method thereof
EP0173490B1 (en) Asphalt or bitumen emulsion
CN110499034A (en) A kind of dedicated modified pitch of pouring asphalt concrete and preparation method thereof
CN1347936A (en) Asphalt modifier and modified asphalt composition
CN109503030A (en) A kind of asphalt preparation method of achievable warm mix
CN102050599A (en) Method for preparing plastic warm-stirred modified asphalt mixture
US5998514A (en) Random vinyl substituted aromatic/C4 -C6 conjugated diolefin polymer modified asphalt mixtures
CN109705587A (en) Rubber powder modified agent, multiplicity reactivation rubber powder and preparation method thereof, composite modified asphalt and preparation method thereof
CN87102886A (en) Aqueous polymerization process is produced the low-molecular weight copolymer of vinyl halide/vinyl-acetic ester
GB2370575A (en) Modified asphalt cement composition

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
C19 Lapse of patent right due to non-payment of the annual fee
CF01 Termination of patent right due to non-payment of annual fee