USPATOLD (U.S. Patents Pre-1976)
Subject
Coverage

U.S. patents in all areas of technology 1790-1975

File Type

Bibliographic, Full text

Features

Thesaurus

National Patent Classification, Cooperative Patent Classification,
International Patent Classification

Alerts (SDIs)

None

CAS Registry®
Number IdentifiersPage Images

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STN AnaVist™

Keep & Share

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

SLART

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STN Easy

Learning Database

Structures

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RecordContent• Full text and classifications for the publications of U.S. patents issued by the United States

File SizeMore than 3.6 million records (12/2015)

Coverage

U.S. patents in all areas of technology 1790-1975

Updates• U.S. Patent Classifications – bimonthly• No new records are added to this database

Language

English

Database
Producer

Univentio Information Services B.V.
De Roysloot 9a2231 NZ Rijnsburg
The Netherlands
Phone: (+31) 71 402 82 62
Fax:(+31) 71 403 53 20
Email: info@univentio.com

Sources

U.S. patents issued by the USPTO from 1790-1975

User Aids• Online Helps (HELP DIRECTORY lists all help messages available)• STNGUIDEPatent and Trademark Office (USPTO)• Complete Chemical Abstracts indexing for one equivalent U.S. chemical patent may
also be included in a record• Patent classifications: NCL, CPC, IPC

December 2015

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USPATOLD

Clusters

•
•
•
•
•
•
•

AUTHORSCASRNSCORPSOURCEENGINEERINGFULLTEXT
HPATENTS
MATERIALS

RelatedDatabases••

USPAT2
USPATFULL

PricingEnter HELP COST at an arrow prompt (=>).

December 2015

• MEDICINE• METALS• PATENTS• PNTTEXT• POLYMERS• USPATALLSTN Database Clusters information (PDF).

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USPATOLD

Search and Display Field Codes
The fields that allow left truncation are marked with an asterisk (*).
Search Field Name

SearchCode

Display
Codes

Search Examples

Basic Index * (contains single
words from the title (TI), CAStitle, abstract (AB), claims (CLM),
and detailed description (DETD)
fields) (1)None (or /BI)S GROWTH REGUL?
S NAPHTHALENE?
S ?ASSAY?

AB, CLM,
DETD, TI, TI.CA

Abstract *

/AB

AB

Accession Number
Application Country
Application Date (2)

/AN
/AC
/AD

Application Number (3)Application Year (2)CAS Registry Number (CAS data)
Claim Text *Classification Code (CAS data)(code and text) (4)

/AP
/AY
/RN
/CLM
/CC

Controlled Term (CAS data)
Cooperative Patent Classification(5,7)
Cooperative Patent Classification,
Action Date
Cooperative Patent Classification,
Combination Sets

/CT
/CPC

S (COBALT(S)CATALYST?)/AB
S ?MODE?/AB
S 1972:58620/AN
S US/AC AND L1
S OCT 4 1938/AD
S 19381004/AD
S US 1901-143434/AP
S 1942/AY
S 400-39-5/RN
S COBALT (S) SALT#/CLM
S 27/CCS HETEROCYCLIC/CCS ANTISTATIC AGENTS/CT
S C12N0009/CPC/CPC.ACD

S 20121113/CPC.ACD

CPC.TAB/CPC.CS

CPC.TAB

Cooperative Patent Classification,
Keywords (7)Cooperative Patent Classification,
VersionCooperative Patent Initial
Classification
Document Type (code and text)
Examiner Name
Field Availability (code and text)/CPC.KW

S (B29C0066-71 (L) B29K2021-00)/CPC.CS
S (B29C0066-71 AND B29K2021-00)/CPC.CS
S C04B0028-04/CPC (T) COMBINATION
SET/CPC.KW
S C12N0009/CPC (S) I/CPC.KW/CPC.VER

S 20130101/CPC.VER

CPC.TAB/CPCIS A61K0006-0014/CPCICPCI/DT (or /TC)
/EXNAM
/FA

DT
EXNAM
Not displayed

File Segment
Index Term (CAS data)

/FS
/IT

International Patent Classification
(5,6)

/IPC

International Patent Classification,
Action Date
International Patent Classification,
Keyword Terms
International Patent Classification,
VersionInventor (1)Inventor Address, City
Inventor Address, Country
Inventor Address, State/IPC.ACDS UTILITY/DT
S ADEE J?/EXNAM
S CA INDEXING/FA
S OS/FAS GRANTED/FSS REACTION OF/IT
S 61849-32-9P/IT
S G03C001/IPC
S G03C001-89/IPC
S ENZYMES/IPC
S 20060101/IPC.ACD/IPC.KWS ADVANCED/IPC.KW

IPC.TAB/IPC.VER

S 20070101/IPC.VER

IPC.TAB/IN (or /AU)
/IN.CTY/IN.CNY/IN.STS KRESS RALPH H?INS ROCHESTER/IN.CTY
S JAPAN/IN.CNY
S NJ/IN.ST

IN
IN, INA
IN, INA
IN, INA

AN
AI
AI
AI
AI
IT, RN
CLM
CCCT, IT
CPC

CPC.TABFS
IT
IPC

IPC.TAB

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USPATOLD

Search and Display Field Codes (cont’d)SearchCode

Search Field Name
Inventor Address, ZIP code (2)IPC, Reclassified
Language (code and text)
Line Count (2)National Patent Classification,
Current, Main and Secondary(5,6)/IN.ZIP/IPCR/LA/LN.CNT/NCL

National Patent Classification,
Current, Main

/NCLM

National Patent Classification
Current, Secondary (5,6)/NCLS

National Patent Classification,
Issue (5,6)/INCL

National Patent Classification,
Issue, Main (5,6)/INCLM

National Patent Classification,
Issue, Secondary (5,6)/INCLS

Other Source (CAS data)
Patent Assignee (1,4)
Patent Country
Patent Kind
Patent Number (3)Patent Number/Kind CodePriority Country
Priority Date (2)/OS/PA (or /CS)
/PC
/PK
/PN
PNK
/PRC
/PRD

Priority Number (3)Priority Year (2)Publication Date (2)Publication Year (2)Reference Patent Country
Reference Patent Number
Section Cross Reference (CASdata) (4)

/PRN
/PRY
/PD
/PY
/RPC
/RPN
/SX

Supplementary Term (CASdata)
Title * (1)

/ST
/TI

Display
Codes

Search Examples
S 44313/IN.ZIP
S B01B001-00/IPCR
S L1 AND EN/LA
S 1000-1500/LN.CNT
S 430529000/NCL
S 430/529.000/NCL
S 430/NCLS ZEOLITES+NT/NCL
S 423121000/NCLM
S 423/NCLM
S ZEOLITES+NT/NCLM
S 423206200/NCLS
S 423/NCLSS ZEOLITES+NT/NCLS
S 264016000/INCLS 264/INCLS ZEOLITES+NT/INCL

IN, INA
IPCR
LA
LN.CNT
NCL

S 433173000/INCLM
S 433/INCLM
S ZEOLITES+NT/INCLM
S 502064000/INCLS
S 502/INCLSS ZEOLITES+NT/INCLS
S 13:10008/OS
S AMERICAN CYANAMID/PA
S US/PC AND L2
S USA/PKS US630001/PN
S US3847871/PNK
S JP/PRCS PRD>=MAR 24 1900
S PRD>=19000324
S GB1916-354203/PRN
S PRY>=1955
S MAR 11 1942/PD
S PY<=1900
S AR/RPCS US211975/RPN
S 1/CC,SXS PHARMACOLOGY/CC,SXS POLYURETHANE?/ST

INCLM

S FILM?/TI
S ?MYCIN?/TI

TI

NCLM

NCLS

INCL

INCLS

OS
PA
PI
PI
PI
PNK
PRAI
PRAI
PRAI
PRAI
PI
PI
REP
REP
CC
ST

(1) Also searches CAS data for this field when available.
(2) Numeric search field that may be searched with numeric operators or ranges.
(3) Either STN or Derwent format may be used.
(4) Search with implied (S) proximity is available in this field.
(5) An online thesaurus is available for this field.
(6) This field is range-searchable in Manual of Classification order. However, it is not a numeric field and may not be searched by using
numeric operators.
(7) When searching combinations of CPC and CPC.KW data, use (S) proximity operator.
December 2015

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USPATOLD

Super Search Fields (1)SearchCode

Search Field Name
Application Number Group (2)Cooperative Patent Classification(2)
Patent Country Group
Patent Number Group (2)FieldsSearched

Display
Codes

Search Examples

/APPS
/CPC

/AP, /PRN/CPCI, /CPCR

S US1964-50545/APPSS C12N0009/CPC

/PCS
/PATS

/PC, /RPC/PN, /RPN

S US/PCSS US630010/PATS

AI, PRAI
CPC, CPCI,
CPCR
PI
PI

(1) Super search fields facilitate crossfile and multifile searching. Enter a super search code to search in one or more fields that may
contain the desired information. EXPAND may not be used with super search fields. Use EXPAND with the individual field codes
instead.
(2) Either STN or Derwent format may be used.

Thesaurus Fields
A thesaurus is present for the National Patent Classification fields (/INCL, /INCLM, /INCLS, /NCL, /NCLM,/NCLS) and the International Patent Classification fields. The classifications and catchwords for the main
headings and subheadings from the 8th edition of the WIPO International Patent Classification (IPC) manual
are available in the /IPC and IPCR fields. The classifications from the previous editions (1-7) are alsoavailable as separate thesauri. To EXPAND and SEARCH in the thesauri for editions 1-8, use the field code
followed by the edition number, e.g., /IC2, /ICM2, /ICS2 for the 2nd edition. Catchwords are included only inthe thesauri for the 8th, 7th, 6th, and 5th editions.
CodeContent

ALL

All associated terms

AUTO (1)HIE

Automatic Relationship (BT, SELF))
Hierarchy (Broader and Narrower Terms(all Broader and Narrower Terms)(BT, SELF, NT)
Complete Title of the SELF Term

TI
BT
KT
NT

Broader Terms(BT, SELF)
Keyword Terms (SELF, KT) (2)Narrower Terms (SELF, NT)NEXT

Next Classification

PREV

Previous Classification

BRO

Complete ClassRT

Related Terms

ExampleE 264016000+ALL/INCL
E A01N025-04+ALL/IPC
E A01N025-04/IPC REL=ON
E 523523000+HIE/NCL
E A01B001-06+HIE/IPC
E 135+TI/NCLM
E A01B001-04+TI/IPC
E 423206200+BT/NCLS
E 423206200+BT/NCLS
E ZEOLITES+KT/NCL
E 264016000+NT/INCL
E A01N025-00+NT/IPC
E 135086000+NEXT15/INCL
E A01B001-16+NEXT5/IPC
E 523523000+PREV3/NCLS
E A01B001-18+PREV5/IPC
E 135019000+BRO5/INCL
E A01B003-14+BRO3/IPC
E A01B001-16+RT/IPC(1) AUTOMATIC relationship is SET OFF. If you SET RELATION ON, the result of EXPAND without any relationship code is the sameas described for AUTO.
(2) Keyword terms are the catchwords corresponding to the USPTO Manual of Classifications subject index headings and subheadings.

December 2015

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USPATOLD

CPC (/CPC) Thesaurus
The Cooperative Patent Classification (CPC) is jointly developed and maintained by the European Patent
Office and the US Patent and Trademark Office. This thesaurus is available in the /CPC search field. All
relationship codes can be used with both the EXPAND and SEARCH commands.
Relationship CodeALL
AUTO (1)
BT
CODE
DEF
HIE

Content

Search Examples

All usually required terms (BT, SELF, CODE, DEF)
Automatic relationship (BT, SELF, CODE, DEF)
Broader terms (BT, SELF)
Classification Code (SELF, CODE)
Definition (SELF, DEF)
Hierarchy terms (all broader and narrower terms) (BT, SELF,
DEF, NT)
Keyword terms (SELF, KT)
All associated terms
Next classification within the same class (SELF, NEXT)
Next n classification within the same class
Narrower terms
Previous Code within the same class (SELF, PREV)
Previous n classifications within the same class
Complete Title of SELF Term and Broader Terms (BT, SELF)

KT
MAX
NEXT
NEXT(n)NT
PREV
PREV(n)TI

E C12M0001-00+ALL/CPC
E G01J003-443+AUTO/CPC
E G01J0003-443+BT/CPC
E CARTRIDGES+CODE/CPC
E B65G0045-16+DEF/CPC
E A01B0001-00+HIE/CPC
E LASER+KT/CPC
E G01J0003-44+MAX/CPC
E A01B0001-24+NEXT/CPC
E A01B0001-24+NEXT3/CPC
E G05B0001-04+NT/CPC
E G05B0019-00+PREV/CPC
E G05B0019-00+PREV2/CPC
E G05B0001-03+TI/CPC(1) Automatic Relationship is SET OFF. In case of SET REL ON the result of EXPAND or SEARCH without any relationship code is thesame as described for AUTO.

Full-Text Browsing
User Request

ExampleSystem Response

DISPLAY BROWSE=> DISPLAY BROWSEENTER (L1) OR L#:.
ENTER (DIS), ANSWER NUMBERS,OR END:NOVICE version

D BRO

EXPERT version

Answer number(s)=> D BRO L1::1-3

Answer number(s) and format
Format only:.
:4 HIT:TI CLM*Format:*KWIC

Forward n fields
Backward n fields
Search forward for a character string:F3:B1:S GROWTH REGUL:S

Search backward for a character
string:S- ALKANOIC ACID:S-End DISPLAY BROWSE

December 2015

:END
=>

display answers 1, 2, and 3 in default
formatdisplay next answer in default format
display answer 4 in HIT format
display title and claim text of lastanswer displayedchange default to KWIC;
no answer displayed
move forward three fields
move backward one fieldsearch forward within record for''growth regul''
repeat search forward for the current
stringsearch backward within record for''alkanoic acid''
repeat search backward for the current
stringexit DISPLAY BROWSE and return toarrow prompt

7
USPATOLDDISPLAY and PRINT Formats
Any combination of formats may be used to display or print answers. Multiple codes must be separated by
spaces or commas, e.g., D L3 1-10 TI,AB or D L3 1-10 TI AB. The fields are displayed or printed in the orderrequested.
Hit-term highlighting is available in all fields except RPN. Highlighting must be on when a SEARCH is
performed to use the FHITSTR, HIT, HITRN, HITSTR, KWIC, and OCC formats.
FormatContent

ExamplesAB
AI (AP) (1)AN (2)CC (SX)
CLM
CPC
CPCI
CPCR
CT (2)DETD
DT (TC)
EXNAM
FS (2)IN (AU)IN.CA
INA (3)
INCLM (2)INCLS (2)IPCR (2)IT
LA (3)
LN.CNT
NCLM (2)NCLS (2)OS
PA (CS)
PA.CA
PI (PN) (1)PNK
PRAI (PRN) (1)REP (RPN)
RN (3)ST
TI (2)
TI.CA

Abstract
Application Information
Accession Number
Classification Code and Section cross-reference (CAS data)
Patent Claim Text
Cooperative Patent Classification
CPC Initial Classification
CPC Reclassification
Controlled Term (CAS data)
Detailed Description
Document Type
Examiner Name
File Segment
Inventor (includes INA)
Inventor (CAS data)
Inventor Address
Issue Main National Patent Classification CodeIssue Secondary National Patent Classification Code
IPC, Reclassification
Index Term (CAS data)
LanguageLine Count
Current Main National Patent Classification CodeCurrent Secondary National Patent Classification CodeOther Source Chemical Abstracts
Patent Assignee (includes PAA and PAT)
Patent Assignee (CAS data)
Patent Information
Patent Number/Kind CodePriority Information
Reference Patent Information
CAS Registry Number (CAS data)
Supplementary Terms (CAS data)
Title
Title (CAS data)

D 1-3 ABD 4 9 AI
D AN
D L3 CC 1-5
D CLM L8
D CPC
D CPCI
D CPCR
D 4 CT
D 1-4 DETD
D DT 2,6-10
D EXNAM 4-8,11
D FS
D IN
D IN.CAD L5 1-4 INA
D 2,5 INCLM
D L2 1-3 INCLS
D L6 7 IPCR
D 1,5,10 IT
D LA
D LN.CNT
D 1-2 NCLM
D 1-5 NCLS
D OS
D 1-3 PA
D 1-3 PA.CA
D PI L8D PNK
D PRAI
D 1-4 REPD RN 2,6-10
D ST
D 2,5 TI
D 2,5 TI.CA

ABS
ALL (1)

D L3 1-5 ABS
D 3 ALL

APPS (1)BIB (1)
CAS
CBIB

AB
AN, TI, IN, INA, PA, PI, AI, PRAI, DT, FS, REP, EXNAM, AB, DETD, CLM,
INCL (INCLM, INCLS), NCL (NCLM, NCLS), CPC (CPCI, CPCR), IPC (IPCR)
AI, PRAI
AN, TI, IN, INA, PA, PI, AI, PRAI, DT, FS, EXNAM, LN.CNT
OS, CC, SX, ST, IT
Compressed bibliographic information

CPC
CPC.TAB
CPC.UNIQDALL (1)

CPCI, CPCR, for the basic patent and patent family members
CPC, CPC.KW, CPC.ACD, CPC.VER in tabular format
Deduplicated list of CPC codes for the patent family
ALL, delimited for postprocessing

D CPC
D CPC.TAB
D CPC.UNIQ
D 1-15 DALLD APPS
D BIB
D CAS 3 L2
D CBIB

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USPATOLDDISPLAY and PRINT Formats (cont’d)Format
FP
FPALL

FPBIB
FHITSTR
CPC.HIT (HITCPC)
HIT
HITRN
HITSTR
IABS
IALL (1)
IBIB (1)
IMAX (1)
INCL (2)IND
IPC (2)
IPC.TAB (2)ISTD (1)
MAX (1)

NCL (2)
PATS (1)
SBIB (1)
SCAN (2,4)
STD (1)

TRIAL (FREE) (2)KWIC
OCC (2)

Content
PI, TI, IN, INA, PA, AI, PRAI, IPC (IPCR), INCL (INCLM, INCLS),
NCL (NCLM, NCLS), CPC (CPCI, CPCR), REP, EXNAM, AB
PI, TI, IN, INA, PA, AI, PRAI, IPC (IPCR), INCL (INCLM, INCLS),
NCL (NCLM, NCLS), CPC (CPCI, CPCR), REP, EXNAM, AB,
DETD, CLM
PI, TI, IN, INA, PA, AI, PRAI, REP, EXNAM
First HIT RN, its text modification, its CA index name, and its
structure diagram
HIT display of CPC code searched
Fields containing hit terms
Hit CAS Registry Number and its text modification
HITRN, its text modification, CA index name, and structure diagram
ABS, with a text label
ALL, indented with text labels
BIB, indented with text labels
MAX, indented with text labels
Issue National Patent Classification Code (INCLM, INCLS)
INCL (INCLM, INCLS), NCL (NCLM, NCLS), CPC (CPCI, CPCR),
IPC (IPCR), OS, CC, SX, ST, IT
International Patent Classifications (IPCR)
IPC in tabular format
STD, indented with text labels
AN, TI, IN, INA, PA, PI, AI, PRAI, DT, FS, REP, EXNAM, AB, DETD,
CLM, INCL (INCLM, INCLS), NCL (NCLM, NCLS), CPC(CPCI, CPCR), IPC (IPCR), OS, CC, SX, ST, IT
Current National Patent Classification Code (NCLM, NCLS)
PI, REPAN, TI, IN, INA, PA, PI, AI, RLI, PRAI, DT, FS, LN.CNT
AN, TI, NCL (NCLM, NCLS), CPC (CPCI, CPCR), IPC (IPCR)(random answer display, no answer number)
AN, TI, IN, INA, PA, PI, AI, PRAI, DT, FS, LN.CNT, INCL (INCLM,
INCLS), NCL (NCLM, NCLS), CPC (CPCI, CPCR), IPC (IPCR)(STD is the default)
AN, TI, INCL (INCLM, INCLS), NCL (NCLM, NCLS), CPC (CPCI,
CPCR), IPC (IPCR)
Up to 20 words before and after hit terms (KeyWord-In-Context)
Number of occurrences of hit terms and fields in which they occur

Examples
D FP
D FPALL 6

D FPBIBD FHITSTR 2
D CPC.HIT or
D HITCPC
D HIT
D HITRND HITSTR 4
D 1-4 IABS
D IALL 2
D IBIB 4-10
D IMAX 1
D 1,5 L4 INCL
D L2 IND 1-4
D 1-4 L2 IPC
D IPC.TABD ISTD 1,5
D MAX L1 1

D 6,12 L1 NCL
D PATS 1-3
D SBIBD SCAND STD 1, 8

D TRIALD KWIC
D OCC(1) By default, patent, application, and priority numbers are displayed in STN format. To display them in Derwent format, enter SET
PATENT DERWENT at an arrow prompt (=>). To reset display to STN format, enter SET PATENT STN.
(2) No online display fee for the format.
(3) Custom display only.
(4) SCAN must be specified on the command line, i.e., D SCAN or DISPLAY SCAN.

December 2015

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USPATOLD

SELECT, ANALYZE, and SORT Fields
The SELECT command is used to create E-numbers containing terms taken from the specified field in ananswer set.
The ANALYZE command is used to create an L-number containing terms taken from the specified field in ananswer set.
The SORT command is used to rearrange the search results in either alphabetic or numeric order of thespecified field(s).

Field Name
Abstract
Accession Number
Application Country
Application Date
Application Information
Application Number
Application Number Group
Application Year
Author (Inventor)
CAS Registry Number (CAS data)
Citation
Claim Text
Classification Code (CAS data)
Controlled Term
CPC Classification
CPC, Initial
CPC, Reclassified
CPC Hit Display
CPC Codes Deduplicated for patent family
Corporate Source (Patent Assignee)
Current Main National Patent Classification CodeCurrent National Patent Classification Code, Main and Secondary
Current Secondary National Patent Classification Code
Detailed Description
Document Type
Examiner Name
Index Term (CAS data)
International Patent Classifications, (All Codes)
Inventor
Inventor (CAS data)
Inventor Address
Inventor Address, City
Inventor Address, Country
Inventor Address, State
Inventor Address, ZIP Code
IPC, First Invention
IPC Reclassification
Issue Main National Patent Classification CodeIssue National Patent Classification Code, Main and Secondary
Issue Secondary National Patent Classification
LanguageLine Count

Field Code
AB
AN
AC
AD
AI
AP
APPS
AY
AU
RN
CIT
CLM
CC
CT
CPC
CPCI
CPCR
CPC.HIT(HITCPC)
CPC.UNIQ
CS
NCLM
NCL
NCLS
DETD
DT
EXNAM
IT
IPC
IN
IN.CA
INA
IN.CTY
IN.CNY
IN.ST
IN.ZIP
IPC.F
IPCR
INCLM
INCL
INCLS
LA
LN.CNTANALYZE/
SELECT (1)

SORT

Y
Y
Y (2)
Y (2)
Y (2,3,4)
Y (2,3)
Y (2,3,5)
Y (2)
Y (6)
Y (2)
Y (2,7)YY
Y (2)Y (17)Y (18)Y (18)
Y

N
N
Y
Y
Y
Y
N
Y
Y
N
N
N
Y
N
N
N
N
Y

Y
Y (8)
Y
Y
Y
Y (9)
Y
Y
Y (2)
Y
Y
Y
N
Y
Y
Y
Y
Y (10)Y (10)
Y
Y
Y
Y
N

Y
Y
Y
Y
N
N
Y
Y
N
N
Y
Y
Y
Y
Y
Y
Y
N
N
Y
Y
N
Y
Y

December 2015

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USPATOLD

SELECT, ANALYZE, and SORT Fields (cont’d)Field Name
Occurrence Count of Hit Terms
Other Source Chemical Abstracts
Other Source Patent Number
Patent Assignee
Patent Assignee (CAS data)
Patent Country
Patent Country Group
Patent Date
Patent Information
Patent Kind
Patent Number
Patent Number Group
Patent Number/Kind CodePatent Year
Priority Country
Priority Date
Priority Information
Priority Number
Priority Year
Reference Patent Country
Reference Patent Information
Reference Patent Number
Section Cross-reference (CAS data)
Supplementary Term (CAS data)
Title
Title (CAS data)
Treatment Code(1)

Field CodeANALYZE/
SELECT (1)

SORT

OCC
OS
OSPN
PA
PA.CA
PC
PCS
PD
PI
PK
PN
PATS
PNK
PY
PRC
PRD
PRAI
PRN
PRY
RPC
REP
RPN
SX
ST
TI
TI.CA
TC

N
Y (2)
Y (2,11)YY
Y (2)
Y (2,12)Y (2)Y (2,3,13)
Y
Y (2,3)
Y (2,3,14)
Y
Y (2)
Y (2)
Y (2)
Y (2,3,15)
Y (2,3)
Y (2)
Y
Y
Y
Y
Y
Y (default)Y
Y (16)

Y
N
N
Y
Y
Y
N
Y
Y
Y
Y
N
N
Y
Y
Y
Y
Y
Y
N
N
N
Y
N
Y
Y
Y

HIT may be used to restrict terms extracted to terms that match the search expression used to create the answer set, e.g., SEL HIT
TI.
(2) SELECT HIT and ANALYZE HIT are not valid with this field.
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Sample Records
DISPLAY IMAXACCESSION NUMBER:
TITLE:INVENTOR(S):PATENT ASSIGNEE(S):1974:75537 USPATOLD Full-text
POLYMERS AND COPOLYMERS OF 1 FERROCENYL 1,3 BUTADIENE
COMBS CSTEPHENS W
WILLIS T
COMBS C,, STEPHENS W,, WILLIS T

PATENT INFORMATION:APPLICATION INFO.:NUMBERKIND
DATE---------------- ------ -------US 3847871
A
19741112
US 1972-252390
19720501

PRIORITY INFORMATION:
DOCUMENT TYPE:
FILE SEGMENT:NUMBER-----------------US 1972-252390
Utility
GRANTED

DATE-------19720511

NUMBERDATE
CLASSINVENTOR--------------- -------- ----------- ----------REFERENCED PATENT:US 3063974
US 3350369
PRIMARY EXAMINER:
LEE, LESTER LBACKGROUND OF THE INVENTION
Field of the Invention This invention relates to a method of using ferrocene so
as to take advantage of its unusual properties. Ferrocene is dicyclopentadienyl
iron, the nucleus of which has been noted for its abilities to absorb
ultraviolet radiation. This unusual property of ferrocene has caused widespreadinterest in utilizing the material as an additive in rubbery polymericmaterials in order to stabilize these materials against degradation of physicalproperties caused by sunlight. In addition, the ferrocene nucleus is highly
stable towards gamma radiation. As a result of these stabilizing properties,
there has been much interest in the use of ferrocene and ferrocene compounds incoatings for space vehicles to protect exposed surfaces.
The use of ferrocene or ferrocene derivatives to achieve the objectives
outlined above has been hampered by the high volatility of ferrocene andferrocene derivatives. The result of this volatility is that when ferrocene isincorporated as an additive to polymeric materials, the high vapor pressure of
the ferrocene causes the material to sublime out of the polymeric matrix
thereby rendering the ferrocene or ferrocene derivative unavailable forstabilizing physical properties.
Description of the Prior Art In general, the solution to the problem ofretaining ferrocene in a polymeric matrix has been to not add ferrocene or
ferrocene derivatives as additives, but rather to include the ferrocene nucleus
in the polymeric material so that it is chemically bonded to the polymer chain
and therefore cannot escape from the rubber or plastic product. In the past,
numerous efforts have been made to find a monomer which can be polymerized, or
copolymerized with a comonomer, without destroying the special properties which
the comonomer would give to the final product. For instance, polymers of
butadiene have certain highly desirable properties such as elongation andtensile strength. If the ferrocene unit is attached to a monomer which is used
in a copolymerization of butadiene, it is possible that the physical propertiesof polybutadiene would be significantly impaired, unless the proper monomer isused. Thus, the use of the proper ferrocene-containing monomer is very
important in achieving the desired properties.
Several polymers and copolymers of ferrocene derivatives have been prepared in
the past. However, most of these polymers were either brittle solids, or wererelatively insoluble and difficult to handle.
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USPATOLD
It is an object of the present invention to provide polymeric materials whichhave ferrocene incorporated in the polymer chemically bonded to the polymericclaim so that the disadvantages inherent in the use of ferrocene as an additive
may be overcome.
It is a further object of this invention to provide liquid polymeric materials
which contain the ferrocene nucleus chemically bonded to the polymer chain.
Another object of this invention is to provide polymeric materials whichcontain the ferrocene nucleus chemically bonded to the polymer chain, whichpolymers are soluble in various solvents and therefore easier to handle.
These, and other objectives of the present invention, are achieved through theuse of l-ferrocenyl-l,3Jbutadiene as a monomer and comonomer with otherpolymerizable materials.
These and other objectives will become more apparent to one skilled in the art
from the following detailed description and examples.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
One of the essential components of this invention is thel-ferrocenyl-l,3-butadiene. This monomer is prepared by a two-step reaction
sequence, the first step of which involves a Grignard reaction ofallylmagnesium halide with ferrocene aldehyde. The reaction product afterhydrolysis is l-ferrocenyl-3-butene-l-ol. This alcohol is then dehydrated bystirring a benzene solution of the alcohol in the presence of aluminum oxide.
More particularly, a solution consisting of grams of ferrocene aldehyde
dissolved in ml. of benzene is added dropwise to a stirred solution of 213
grams of allylmagnesium bromide in 1200 ml. of ether under reflux. Refluxing
and stirring are continued for two hours after the addition is completed. The
reaction mixture is then allowed to cool to room temperature and is poured into
ml. of a cold 10% solution of ammonium chloride in water containing grams of
sodium disulfate in order to eliminate the impurities in the Grignard reagent.
The mixture is then filtered and the organic layer from the filtrate isevaporated yielding 219 grams of l-ferrocenyl3-butene-l-ol.
This reaction product is stirred with 2.2 kg. of acidic aluminum oxide (Ventron
Acidic Alumina of Ventron Corporation) in 3.2 liters of benzene for one hour to. dehydrate the alcohol. The aluminum oxide is then removed by filtration andl-ferrocenyl-l,3-butadiene, a red solid, is recovered by evaporation of thesolvent.
Polymers of l-ferrocenyl-l,3-butadiene may be made by treating the monomer with
an appropriate catalyst with solvent. Copolymers of l-ferrocenyl-l.S-lmtadiene
with dienes may be made by treating a mixture of the two monomers with anappropriate catalyst. Also, copolymers of l-ferrocenyl-l,3-butadiene withesters of acrylic acid may likewise be prepared by treatment of a mixture of .
the monomers with or without solvent with a suitable polymerization catalyst.
Furthermore, copolymers of 1ferrocenyl-l,3-butadiene with vinyl ketones, vinyl
ethers, and vinyl ferrocene may be made by treatment of a mixture of the twomonomers with or without solvent with a suitable polymerization catalyst.
The following examples illustrate the preparation of the polymers andcopolymers of the present invention.
EXAMPLE IA polymer of 1-ferrocenyl-1,3-butadiene was prepared by dissolving thel-ferrocenyl-l,3-butadiene in ethyl ether and then adding a trace of sulfuric
acid as the catalyst. Instantaneous polymerization occurred at room
temperature. The solvent was then evaporated and the product purified bywashing, leaving a brittle yellow solid polymer of l-ferrocenyl-l,3-butadiene
which was soluble in methylene chloride. That the polymer actually resulted wasproven by (1) thin layer chromatography and (2) evacuation under high vacuum.
Thin layer chromatography (TLC) is performed by dissolving a sample of the
December 2015

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reaction product in a small amount of solvent in a test tube and placing asmall spot of the solution on the bottom of a TLC plate. The plates used inthis test were supplied by Brinkman Instruments Company and are MN Silica-gel
S-HR/UV254 chromatographic plates, and the solvent was a mixture of hexane andacetone. Monomeric molecules, such as any unreacted (i.e. unpolymerized)
l-ferrocenyl-l,3-butadiene, are carried up the chromatographic strip as asingle spot moving slightly behind the solvent front as it climbs the strip.
When polymers are present, these materials are moved much more slowly, andusually appear as a continuous smear with a dark brown streak all the way fromthe origin up to approximately half the distance to the solvent front. Since
the polymer molecular weights are significantly higher than the molecularweights of the monomers involved, the migration rates of the polymers would be
expected to be much lower, and therefore these materials "" would not be foundas high on the chromatographic plate. In addition, since the polymeric products
are generally mixtures of molecules of different molecular weights the polymer
appears as a smear, or a streak, rather than as a single spot as in the case of
the monomer or simple low molecular weight compounds. The TLC plates weredeveloped by exposure to an iodine atmosphere. The brittle yellow solid polymerof this example produced a chromatographic plate with a smear which proved thatthe polymerization had occurred.
Evacuation under high vacuum is performed by subjecting samples recovered fromthe polymerization reaction mixtures to a vacuum of less than one millimeter at
a temperature of C. Under these conditions, the lower molecular weightmaterials are sublimed and lost by evaporation into the cold trap in the vacuum
system. Anything which is not lost by this process necessarily has a muchhigher molecular weight, and is therefore polymeric. The polymer of thisexample acted as expected g under the vacuum, thereby proving thatpolymerization occurred.
The molecular weight of the resultant polymer was found to be 2,737 by vapor
pressure osmometry.
The iron content of the resultant polymer was found to g be 23.15% whichcorresponds closely to the theoretical value of 23.3%.
EXAMPLE II A polymer of l-ferrocenyl-l,3-butadiene was prepared by a different
process. The monomer was dissolved in methylene chloride and cooled to -79 C. A
trace amount of boron trifluoride etherate was added and the mixture wasstirred for approximately minutes. The catalyst was destroyed by the additionof ammonium 6i chloride, whereupon the polymeric product was obtained byfiltering the mixture, evaporating the solvents, dissolving the product inethyl ether, and precipitating it with methanol. The product was a brittle
yellow solid polymer of l-ferrocenyl-l,3-butadiene which is soluble inmethylene chloride and ethyl ether. Evacuation under high vacuum and TLC as
described in Example I proved that a polymer actually formed.
The polymer had an iron content of 22.48%, and a molecular weight of 2,780.
EXAMPLE III
In a third process for polymerizing l-ferrocenyl-1,3butadiene grams of themonomer, ml. water, 0.2 g. potassium persulfate, and 0.5 g. sodium laurylsulfate were combined and these ingredients were heated at C. for four hours.
The polymeric product was precipitated by the addition of a sodium chloride
solution. The precipitate was dissolved in benzene and reprecipitated with .
methanol yielding a soluble yellow-orange solid polymer ofl-ferrocenyl-l,3-butadiene, the existence of which was proven by TLC and highvacuum evacuation as described in Example I.
The poly-l-ferrocenyl-1,3 - butadiene of this Example had a molecular weight of
2,814 and an iron content of 22.17%.
EXAMPLE IV A copolymer of l-ferrocenyl-l,3-butadiene and isoprene was preparedby adding grams of each of the monomers, 1.6 grams of potassium persulfate, and
4. grams of sodium lauryl sulfate to ml. of water. The mixture was stirred andheated at C. for four hours. The reaction mixture was allowed to cool and thenDecember 2015

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was >r extracted with benzene. A viscous (tar-like consistency) orange-red
liquid polymer was obtained by precipitation with methanol. Evacuation underhigh vacuum and TLC as described in Example I proved that a copolymer formed.
The resultant copolymer had a molecular weight of 1,695.
An analysis of the iron content of the copolymer showed 20.2% iron as opposed
to a homopolymer iron content of 23.3%. Therefore, the resultant polymericproduct was comprised of approximately 86% 1-ferrocenyl-l,3-butadiene monomer
and approximately 14% isoprene.
EXAMPLE V A copolymer of l-ferrocenyl-l,3-butadiene and butadiene was formed inthis example. Butadiene (120 grams), l-ferrocenyl-l,3-butadiene (40 grams),
4,4-azobis-(4cyanopentanoic acid) (13 grams), and dioxane (320 ml.) werestirred at C. in a sealed bomb for four days. The g solvent was removed in a
vacuum and the product was precipitated from ethyl ether with methanol. The
product was an orange-red liquid copolymer the existence of which was again
proven by TLC and high vacuum evacuation, as described in Example I.
n The molecular weight of the resultant copolymer was 3,200.
The chemical analysis of the copolymer showed 12.3% iron, a fact whichindicates that a copolymer composed of about weight percent
l-ferrocenyl-l,3-butadiene and g about weight percent butadiene was formed.
EXAMPLE VI A copolymer of l-ferrocenyl-l,3-butadiene and methyl acrylate wasprepared by stirring methyl acrylate (10 grams), l-ferrocenyl-l,3-butadiene (10grams), 4,4-azobis-(4-cyanopentanoic acid) (1.3 grams), and dioxane (80 ml.)
under nitrogen for four days at to C. The dark red liquid polymeric product was
obtained by precipitation from ether with methanol. TLC and high vacuum
evacuation showed the existence of the copolymer as was done in Example I.
EXAMPLE VII _ A copolymer of l-ferrocenyl-l,3-butadiene and methyl vinyl ketone
was formed by dissolving equal quantities of the two monomers in a six-foldvolume of hexane. A trace of sulfuric acid was added to the mixture at 0 C. The
reaction mixture was allowed to stand .for five minutes and the solvent wasevaporated yielding a red oily copolymer > of l-ferrocenyl-l,3-butadiene andmethyl vinyl ketone.
3,847, TLC and high vacuum evacuation showed the existence of the copolymer, as
described in Example I.
EXAMPLE VIII A copolymer of l-ferrocenyl-l,3-butadiene and vinyl g isobutyl
ether was prepared. Equal amounts of 1-ferrocenyl-l,3-butadiene and vinyl
isobutyl ether were dissolved in a six-fold volume of hexane. A trace amount ofsulfuric acid was added to the mixture at 0 C. The mixture was then allowed tostand for approximately five minutes. The solvent was next evaporated yielding
a viscous red copolymer of 1 - ferrocenyl-l,3-butadiene and vinyl isobutyl
ether. TLC and high vacuum evacuation showed the existence of the copolymer, as
described in Example I.
EXAMPLE IX A copolymer of l-ferrocenyl-l,3-butadiene and vinyl ferrocene wasprepared by heating grams of each of the monomers with 0.5 grams of potassium
persulfate, grams of sodium lauryl sulf ate, and ml. of water with 2 0.3 gramsof acrylic acid at C. for three hours. The reaction mixture was precipitated,washed, dissolved in ether, and reprecipitated with methyl alcohol, yielding aclear red-orange plastic polymer. TLC and high vacuum evacuation showed theexistence of the copolymer as was described in Example I.
The resultant copolymer had a molecular weight of 1,236.
It is to be understood that the foregoing examples and description are for the
purposes of illustration only, and that various changes may be made therein
without departing from the spirit and scope of the invention.
What is claimed is:What is claimed is:
December 2015

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USPATOLD
1. As a composition of matter, homopolymers of 1ferrocenyl-l,3-butadieneprepared by reacting 1-ferrocenyl-l,3-butadiene with a catalyst, in thepresence of a solvent, at a temperature of from about -79 to C., for a periodof from about 1 minute to 4 hours.
2. As a composition of matter, copolymers of 1-ferrocenyl-l,3-butadiene and acomonomer selected from the group consisting of dienes, acrylic acid, vinyl
ketones, vinyl ethers, and vinyl ferrocene, prepared by reacting
1ferrocenyl-l,3-butadiene and a comonomer with a catalyst, in the presence of asolvent, at a temperature of from about 0 to C., for a period of from about 5
minutes to 4 days.
3. The copolymers of claim 2 wherein the diene is isoprene.
4. The copolymer of claim 2 wherein the diene is butadiene.
5. The copolymer of claim 2 wherein the ester of acrylic acid is methyl
acrylate.
6. The copolymer of claim 2 wherein the vinyl ketone is methyl vinyl ketone.
7. The copolymer of claim 2 wherein the vinyl ether is vinyl isobutyl ether.
8. The product produced by dissolving 1-ferrocenyl1,3-butadiene in ethyl ether,adding sulfuric acid at room temperature, subsequently evaporating the ether,and purifying the product by washing.
9. The product produced by dissolving 1-ferrocenyll,3jbutadiene in methylene
chloride, cooling the mixture to -79 C., adding boron trifluoride etherate,stirring the mixture for minutes, adding ammonium chloride, filtering the
mixture, evaporating the methylene chloride, dissolving the product in ethyl
ether, and precipitating it with methanol.
10. The product produced by combining 1-ferrocenyl1,3-butadiene, water,
potassium persulfate, and sodium lauryl sulfate; heating these ingredients at
C. for four hours; precipitating the product by the addition of sodium
chloride; dissolving the precipitate in benzene; and reprecipitating the
product with methanol.
11. The product produced by combining equal amounts ofl-ferrocenyl-l,3-butadiene and isoprene with potassium persulfate, sodium
lauryl sulfate, and water; stirring the mixture; heating at C. for four hours;
cooling the reaction mixture; and extracting the product with benzene.
12. The product produced by combining butadiene, 1ferrocenyl-l,3-butadiene,
4,4-azobis-(4 - cyanopentanoic acid) and dioxane; stirring at C. in a sealedbomb for four days; removing the solvent in a vacuum; and precipitating the
product from ethyl-ether with methanol.
13. The product produced by stirring methyl acrylate,l-ferrocenyl-l,3-butadiene, 4,4-azobis-(4-cyanopentanoic acid), and dioxane
under nitrogen for four days at to 70 C.; and precipitating the polymericproduct from, ether with methanol.
14. The product produced by dissolving 1-ferrocenyl1,3-butadiene and methyl
vinyl ketone in hexane; adding sulfuric acid to the mixture at 0 C.; allowing
the mixture to stand for 5 minutes; evaporating the solvent; and purifying the
product by washing.
15. The product produced by dissolving 1-ferrocenyl1,3-butadiene and vinyl
isobutyl ether in hexane; adding sulfuric acid to the mixture at 0 C.; allowing
the mixture to stand for 5 minutes; evaporating the solvent to yield the
product; and purifying the product by washing.
16. The product produced by heating l-ferrocenyl-1,3butadiene, vinyl ferrocene,
potassium persulfate, sodium lauryl sulfate, water, and acrylic acid at C. for
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USPATOLD
three hours; precipitating the mixture; washing the product; dissolving the
product in ether; and reprecipitating the product with methyl alcohol.
ISSUE U.S. PATENT CLASSIF.:
MAIN:
526/204.000
SECONDARY:
524/175.000; 526/214.000; 526/219.000; 526/225.000;
526/229.000; 526/234.000; 526/236.000; 526/237.000;
526/238.000; 526/241.000; 526/329.100; 526/332.000;
526/337.000
CURRENT U.S. PATENT CLASSIF.:
MAIN:
526/204.000
SECONDARY:
524/175.000; 526/214.000; 526/219.000; 526/225.000;
526/229.000; 526/234.000; 526/236.000; 526/237.000;
526/238.000; 526/241.000; 526/329.100; 526/332.000;
526/337.000
COOP. PATENT CLASSIF.:
INITIAL:
C08F0036-04 [I]INT. PATENT CLASSIF.:
RECLASS:
C08F0036-04 [I]
CHEMICAL ABSTRACTS DATA-----------------------COPYRIGHT 2013 ACS on STN

PATENTKIND
DATE---------------- ---- -------OS
82:98815* 1975:98815
US 3847871* CA Data for this record included
CA CLASSIF.:
35-3 (Synthetic High Polymers)
SUPPL. TERM:
ferrocenylbutadiene polymn
INDEX TERM:
Polymerization(of ferrocenylbutadiene)
INDEX TERM:
32613-29-9P
52953-54-5P
54633-59-9P
54633-61-3P
54633-62-4P
54787-80-3P(manufacture of)54633-60-2P

DISPLAY TI TI.CA IN IN.CA PA PA.CA
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IN.CA
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BITUMINOUS COMPOSITIONS CONTAINING PLASTIC OR ELASTOMER POLYSULPHIDEPOLYMERS
Bitumen preparation containing organic polysulfides
GARRIGUES CNICOLAU A
SIGNOURET J
Garrigues, Claude; Nicolau, Albert; Signouret, Jean Baptiste
SOCIETE NATIONALE DES PETROLES D AQUITAINE
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